CN109208380A - Using the paper of Cypres - Google Patents

Using the paper of Cypres Download PDF

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Publication number
CN109208380A
CN109208380A CN201811278570.1A CN201811278570A CN109208380A CN 109208380 A CN109208380 A CN 109208380A CN 201811278570 A CN201811278570 A CN 201811278570A CN 109208380 A CN109208380 A CN 109208380A
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China
Prior art keywords
starch
paper
mixing
fermentation
cypres
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Granted
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CN201811278570.1A
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CN109208380B (en
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不公告发明人
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Binzhou Kechuang Incubator Co ltd
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08BPOLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B31/00Preparation of derivatives of starch
    • C08B31/003Crosslinking of starch
    • C08B31/006Crosslinking of derivatives of starch
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F251/00Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C12BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00Preparation of compounds containing saccharide radicals
    • C12P19/04Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21BFIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00Fibrous raw materials or their mechanical treatment
    • D21B1/04Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/30Defibrating by other means
    • D21B1/36Explosive disintegration by sudden pressure reduction
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00Pulping cellulose-containing materials
    • D21C3/02Pulping cellulose-containing materials with inorganic bases or alkaline reacting compounds, e.g. sulfate processes
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/21Macromolecular organic compounds of natural origin; Derivatives thereof
    • D21H17/24Polysaccharides
    • D21H17/28Starch
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/20Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00Coated paper; Coating material
    • D21H19/10Coatings without pigments
    • D21H19/14Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • D21H19/24Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16Sizing or water-repelling agents
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/02Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
    • D21H23/22Addition to the formed paper
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H27/00Special paper not otherwise provided for, e.g. made by multi-step processes

Abstract

The present invention relates to the paper using Cypres.The preparation method is that: after mixing by starch and sodium periodate solution and vibrate impregnation, filtering, separation, it is dried to obtain pretreated starch, it is mixed with water, heat temperature raising stirs to get mixed liquor, it adjusts pH and epoxychloropropane is added dropwise, it is stirred to react to obtain crosslinked starch, after butyl acrylate mixing is added, add potassium peroxydisulfate, insulation reaction obtains sizing agent crude product, again by rapeseed dregs after Steam explosion treatment, it is boiled with sodium hydroxide solution heating, mixing is obtained by filtration and cooks liquid, fermentation substrate is obtained after the mixing of sizing agent crude product is added, add bacillus subtilis bacteria suspension, after sealing and fermenting, through high-temperature sterilization, it is concentrated to get modified starch base Cypres.The beneficial effects of the present invention are: modified starch base Cypres water-resistance of the present invention is strong and viscosity is high, it is worthy to be popularized and uses.

Description

Using the paper of Cypres
Technical field
The present invention relates to sheet processing technical fields, and in particular to using the paper of Cypres.
Background technique
In recent years, global soil erosion, desertification, agricultural product castoff arbitrarily abandon waste, and food shortage is more next More serious, in response to world's strategy of sustainable development demand, paper raw material sources increasingly limit in paper industry, in addition Enhancing of the people to environmental consciousness, the raw material based on the pervious timber gradually become with to waste paper recycle and reuse for It is main.Paper is recycled by multiple repetition, and the fiber of paper pulp will shorten, intensity is deteriorated, in this way at the paper performance of paper, Quality all can be very poor, and the requirement with people to paper performance, Safety and Environmental Protection is continuously improved, and develops high effective green environmentally friendly Cypres become enterprise's technical problem urgently to be resolved.
Starch has that source is wide, spy similar with paper fibre structure in environmentally friendly, relative low price, structure Point is common Cypres, but ring crush intensity, bursting strength are low after common ative starch primary surface sizing agent.In State number of patent application CN201310272481.7 discloses a kind of preparation method of Cypres, and this method is by starch at Reason, oxidation, dissolution, gelatinization, storage, addition auxiliary agent, Process of Applying Glue, obtain Cypres.It is helped by oxidized starch and addition Agent improves the sizing efficiency to paper, all has greatly improved to the overall performance of paper, efficiently solves ring pressure after sizing The low problem of intensity, bursting strength, but that there are water-resistance is poor, and viscosity is small, easily infiltrates into paper, is unfavorable for sizing agent in paper table The defect of face film forming.
Therefore, a kind of water-resistance is strong and viscosity is high modified starch base Cypres are invented to sheet processing technical field With positive meaning.
Summary of the invention
Present invention mainly solves the technical issues of, poor for current starch base Cypres water-resistance, viscosity is small, be easy It penetrates into paper, is unfavorable for the defect that sizing agent forms a film in paper surface, provide a kind of modified starch base Cypres Preparation method.
In order to solve the above-mentioned technical problem, the technical scheme adopted by the invention is that:
(1) 30~40min of impregnation, filtering, isolated filter residue, by institute are vibrated after mixing starch and sodium periodate solution Filter residue and drying is obtained, pretreated starch is obtained;
(2) above-mentioned pretreated starch and water are mixed, is heated to 40~50 DEG C, stirs to get mixed liquor, is adjusted with hydrochloric acid PH of mixed is to 5.5~6.5, then epoxychloropropane is added dropwise into mixed liquor, is heated to 50~60 DEG C, it is stirred to react 3~ 5h obtains crosslinked starch;
(3) it is fitted into reaction kettle after mixing butyl acrylate and above-mentioned crosslinked starch, then potassium peroxydisulfate is added into reaction kettle, 70~80 DEG C, 2~4h of insulation reaction are heated to, sizing agent crude product can be obtained after its cooled to room temperature, it is spare;
(4) rapeseed dregs is weighed, Steam explosion treatment obtains explosion rapeseed dregs, then explosion rapeseed dregs and sodium hydroxide solution are mixed Heating is boiled after conjunction, and filtering removal filter cake, gained filtrate is that mixing cooks liquid;
(5) spare sizing agent crude product and above-mentioned mixing are cooked after liquid mixes and obtains fermentation substrate, fermentation substrate is packed into and is sent out In fermentation tank, then bacillus subtilis bacteria suspension is added into fermentor, is sealed by fermentation;
(6) to it is above-mentioned after fermentation, take out tunning high-temperature sterilization, obtain sterilization fermentation product, then sterilization fermentation is produced Object concentration, gained concentrate is modified starch base Cypres.
Starch as described in step (1) is cornstarch, wheaten starch, konjak starch, any one in potato starch.
The mass ratio of starch and sodium periodate solution as described in step (1) is 1:10, the quality point of sodium periodate solution Number is 10%.
The mass ratio of pretreated starch described in step (2) and water is 1:5, and the additional amount of epoxychloropropane is pretreatment The 5% of starch quality.
The mass ratio of butyl acrylate described in step (3) and crosslinked starch is 1:2, and the additional amount of potassium peroxydisulfate is to hand over Join the 4~5% of starch quality
The pressure of Steam explosion treatment described in step (4) is 2.0~2.5MPa, time of Steam explosion treatment is 10~ The mass ratio of 15min, explosion rapeseed dregs and sodium hydroxide solution is 1:8, and the mass fraction of sodium hydroxide solution is 10%, heating Boiling time is 20~30min.
The mass ratio that sizing agent crude product described in step (5) and mixing cook liquid is 5:1, bacillus subtilis bacteria suspension Additional amount be the 5% of fermentation substrate quality, the concentration of bacillus subtilis bacteria suspension is 107cfu/mL, the temperature of sealing and fermenting It is 40~50 DEG C, the time of sealing and fermenting is 5~7 days.
High-temperature sterilization temperature described in step (6) is 120~130 DEG C, and the high-temperature sterilization time is 10~15min, concentration Concentrate volume afterwards is the 1/3 of sterilization fermentation product original volume.
The beneficial effects of the present invention are:
(1) starch surface hydroxyl abundant is oxidized to carboxyl with sodium periodate solution first by the present invention, is made with epoxychloropropane The oxygen atom of epoxychloropropane epoxy group is protonated, converts work for epoxide in acid condition for crosslinking agent Property very strong protonation epoxide, it is reacted with the carboxyl on oxidized starch surface generates ester bond, obtain crosslinked starch, this On the one hand process reduces starch surface polarity hydroxyl quantity and hydrophily carboxyl quantity, on the other hand produce hydrophobicity ester Key effectively increases the hydrophobic performance of starch, uses it as sizing agent raw material, improves the water repelling property of sizing agent;
(2) present invention has imported appropriate firm cross-linking chemistry during with epoxychloropropane crosslinked starch into starch Hydrogen bond between key, and the active group on starch surface constitutes the crosslinked starch with multidimensional reticular structure, improves starch Viscosity, make it be not easy to penetrate into paper, be advantageously used for the film forming of sizing agent, in addition by after crosslinking starch and film forming it is splendid Butyl Acrylate Monomer cause polymerization, obtain modified starch, further improve the film forming and viscosity of sizing agent;
(3) present invention is by the residue rapeseed dregs Steam explosion treatment after oil expression, under the conditions of certain steam pressure and temperature, Cellulose and hemicellulose fraction in rapeseed dregs are degraded to low molecule carbohydrate, these carbohydrates are in blasting process through pressure and temperature Chemical change occurs for the effect of degree, generates Furnan products, soda boiling system is then added into the rapeseed dregs after explosion, so that alkali soluble Property lignin degradation, resinous polymer can be generated with Furnan products, itself and modified starch are mixed, shallow lake can be improved The viscosity of powder, in addition remaining rapeseed oil degrades under the action of microorganism and generates hydrophobicity ester group in rapeseed dregs, and passes through life Object self-crosslinking is introduced into sizing agent, so that the water-resistance of sizing agent further increases, is had broad application prospects.
Specific embodiment
It in mass ratio be first 1:10 by starch and mass fraction is to be placed on shaking table after the mixing of 10% sodium periodate solution to shake 30~40min of impregnation is swung, is filtered after vibrating impregnation, gained filter residue is put into baking oven and existed by isolated filter residue Dry 20~30min, obtains pretreated starch at 50~60 DEG C;Pretreated starch and water are mixed for 1:5 in mass ratio again, added Heat is warming up to 40~50 DEG C, and 15~20min of stirring obtains mixed liquor, and mixed liquor is packed into blender, three mouthfuls of thermometer It is that 0.5mol/L hydrochloric acid adjusts pH of mixed to 5.5~6.5, then pretreated starch is added dropwise into mixed liquor with concentration in flask The epoxychloropropane of quality 5% is heated to 50~60 DEG C, is stirred to react 3~5h, obtains crosslinked starch;Then in mass ratio For 1:2 will butyl acrylate and crosslinked starch mix after is fitted into reaction kettle, then into reaction kettle addition crosslinked starch quality 4~ 5% potassium peroxydisulfate, is heated to 70~80 DEG C, and 2~4h of insulation reaction can be obtained after its cooled to room temperature and apply Jelly crude product;Rapeseed dregs is weighed to be put into steam blasting machine, under conditions of burst pressure is 2.0~2.5MPa, steam blasting 10~15min is handled, obtains explosion rapeseed dregs, then explosion rapeseed dregs and mass fraction are pressed into quality for 10% sodium hydroxide solution Than boiling 20~30min, filtering removal filter cake for heating after 1:8 mixing, gained filtrate is that mixing cooks liquid;It is again that sizing agent is thick It is to obtain fermentation substrate after 5:1 mixing that product and mixing cook liquid in mass ratio, fermentation substrate is fitted into fermentor, then to fermentation The concentration of fermentation substrate quality 5% is added in tank for 107cfu/mL bacillus subtilis bacteria suspension, 40~50 after sealing tank mouth Heat-preservation fermentation 5~7 days at DEG C;It is finally put into high-temperature sterilization box, is heated to after fermentation, take out tunning 120~130 DEG C, 10~15min of high-temperature sterilization, sterilization fermentation product is obtained, then sterilization fermentation product is put into vacuum concentration pot In, concentration pressure inside the tank is reduced to 1000~1200Pa, is concentrated into 1/3 that concentrate volume is sterilization fermentation bulk product, institute Obtaining concentrate is modified starch base Cypres.The starch is cornstarch, wheaten starch, konjak starch, potato Any one in starch.
Example 1
It in mass ratio be first 1:10 by starch and mass fraction is that oscillation leaching on shaking table is placed on after 10% sodium periodate solution mixes Stain handles 30min, filters after vibrating impregnation, isolated filter residue, and it is dry at 50 DEG C that gained filter residue is put into baking oven Dry 20min, obtains pretreated starch;Pretreated starch and water are mixed for 1:5 in mass ratio again, 40 DEG C is heated to, stirs It mixes 15min and obtains mixed liquor, mixed liquor is fitted into the three-necked flask for having blender, thermometer, is 0.5mol/L with concentration Hydrochloric acid adjusts pH of mixed to 5.5, then the epoxychloropropane of pretreated starch quality 5% is added dropwise into mixed liquor, is heated to 50 DEG C, it is stirred to react 3h, obtains crosslinked starch;Then it is filled after in mass ratio mixing butyl acrylate and crosslinked starch for 1:2 Enter in reaction kettle, then the potassium peroxydisulfate of crosslinked starch quality 4% is added into reaction kettle, is heated to 70 DEG C, insulation reaction Sizing agent crude product can be obtained in 2h after its cooled to room temperature;It weighs rapeseed dregs to be put into steam blasting machine, in burst pressure Under conditions of power is 2.0MPa, Steam explosion treatment 10min obtains explosion rapeseed dregs, then by explosion rapeseed dregs and mass fraction It is in mass ratio that 20min is boiled in heating after 1:8 is mixed for 10% sodium hydroxide solution, filtering removal filter cake, gained filtrate is to mix Cook liquid;It is to obtain fermentation substrate after 5:1 is mixed that sizing agent crude product and mixing are cooked liquid again in mass ratio, and fermentation substrate is filled Enter in fermentor, then it is 107cfu/mL bacillus subtilis bacteria suspension that the concentration of fermentation substrate quality 5%, which is added, into fermentor, Seal tank mouth after at 40 DEG C heat-preservation fermentation 5 days;Finally it is put into high-temperature sterilization box to after fermentation, take out tunning, 120 DEG C, high-temperature sterilization 10min are heated to, obtains sterilization fermentation product, then sterilization fermentation product is put into vacuum concentration pot In, concentration pressure inside the tank is reduced to 1000Pa, is concentrated into 1/3 that concentrate volume is sterilization fermentation bulk product, gained concentration Object is modified starch base Cypres.The starch is cornstarch.
Example 2
It in mass ratio be first 1:10 by starch and mass fraction is that oscillation leaching on shaking table is placed on after 10% sodium periodate solution mixes Stain handles 35min, filters after vibrating impregnation, isolated filter residue, and it is dry at 55 DEG C that gained filter residue is put into baking oven Dry 25min, obtains pretreated starch;Pretreated starch and water are mixed for 1:5 in mass ratio again, 45 DEG C is heated to, stirs It mixes 18min and obtains mixed liquor, mixed liquor is fitted into the three-necked flask for having blender, thermometer, is 0.5mol/L with concentration Hydrochloric acid adjusts pH of mixed to 6.0, then the epoxychloropropane of pretreated starch quality 5% is added dropwise into mixed liquor, is heated to 55 DEG C, it is stirred to react 4h, obtains crosslinked starch;Then it is filled after in mass ratio mixing butyl acrylate and crosslinked starch for 1:2 Enter in reaction kettle, then the potassium peroxydisulfate of crosslinked starch quality 5% is added into reaction kettle, is heated to 75 DEG C, insulation reaction Sizing agent crude product can be obtained in 3h after its cooled to room temperature;It weighs rapeseed dregs to be put into steam blasting machine, in burst pressure Under conditions of power is 2.3MPa, Steam explosion treatment 13min obtains explosion rapeseed dregs, then by explosion rapeseed dregs and mass fraction It is in mass ratio that 25min is boiled in heating after 1:8 is mixed for 10% sodium hydroxide solution, filtering removal filter cake, gained filtrate is to mix Cook liquid;It is to obtain fermentation substrate after 5:1 is mixed that sizing agent crude product and mixing are cooked liquid again in mass ratio, and fermentation substrate is filled Enter in fermentor, then it is 107cfu/mL bacillus subtilis bacteria suspension that the concentration of fermentation substrate quality 5%, which is added, into fermentor, Seal tank mouth after at 45 DEG C heat-preservation fermentation 6 days;Finally it is put into high-temperature sterilization box to after fermentation, take out tunning, 125 DEG C, high-temperature sterilization 13min are heated to, obtains sterilization fermentation product, then sterilization fermentation product is put into vacuum concentration pot In, concentration pressure inside the tank is reduced to 1100Pa, is concentrated into 1/3 that concentrate volume is sterilization fermentation bulk product, gained concentration Object is modified starch base Cypres.The starch is wheaten starch.
Example 3
It in mass ratio be first 1:10 by starch and mass fraction is that oscillation leaching on shaking table is placed on after 10% sodium periodate solution mixes Stain handles 40min, filters after vibrating impregnation, isolated filter residue, and it is dry at 60 DEG C that gained filter residue is put into baking oven Dry 30min, obtains pretreated starch;Pretreated starch and water are mixed for 1:5 in mass ratio again, 50 DEG C is heated to, stirs It mixes 20min and obtains mixed liquor, mixed liquor is fitted into the three-necked flask for having blender, thermometer, is 0.5mol/L with concentration Hydrochloric acid adjusts pH of mixed to 6.5, then the epoxychloropropane of pretreated starch quality 5% is added dropwise into mixed liquor, is heated to 60 DEG C, it is stirred to react 5h, obtains crosslinked starch;Then it is filled after in mass ratio mixing butyl acrylate and crosslinked starch for 1:2 Enter in reaction kettle, then the potassium peroxydisulfate of crosslinked starch quality 5% is added into reaction kettle, is heated to 80 DEG C, insulation reaction Sizing agent crude product can be obtained in 4h after its cooled to room temperature;It weighs rapeseed dregs to be put into steam blasting machine, in burst pressure Under conditions of power is 2.5MPa, Steam explosion treatment 15min obtains explosion rapeseed dregs, then by explosion rapeseed dregs and mass fraction It is in mass ratio that 30min is boiled in heating after 1:8 is mixed for 10% sodium hydroxide solution, filtering removal filter cake, gained filtrate is to mix Cook liquid;It is to obtain fermentation substrate after 5:1 is mixed that sizing agent crude product and mixing are cooked liquid again in mass ratio, and fermentation substrate is filled Enter in fermentor, then it is 107cfu/mL bacillus subtilis bacteria suspension that the concentration of fermentation substrate quality 5%, which is added, into fermentor, Seal tank mouth after at 50 DEG C heat-preservation fermentation 7 days;Finally it is put into high-temperature sterilization box to after fermentation, take out tunning, 130 DEG C, high-temperature sterilization 15min are heated to, obtains sterilization fermentation product, then sterilization fermentation product is put into vacuum concentration pot In, concentration pressure inside the tank is reduced to 1200Pa, is concentrated into 1/3 that concentrate volume is sterilization fermentation bulk product, gained concentration Object is modified starch base Cypres.The starch is potato starch.
Reference examples: the Cypres of Weifang company production.
The Cypres of modified starch base Cypres obtained by above-described embodiment and reference examples are detected, specifically It detects as follows:
Paper is cut into the scraps of paper of 20cm × 18cm, is layered on level board, then by modified starch base top sizing obtained by embodiment The Cypres of agent and reference examples are respectively coated in sheet surface, resin added 3g/m2, coating finishes, be placed at room temperature from It so dries, and the tabula rasa that the sizing face of the scraps of paper is close to above photo dryer is put into constant-temperature constant-humidity environment after 90s is dried Middle equilibrium water conten, the paper after sizing is made.
1, it viscosity: is measured using NDJ-1 type rotary viscometer;
2, the paper after sizing water-resistance: is determined half under conditions of constant temperature and humidity (22~24 DEG C of humidity 49~51% of temperature) Diameter is the circular paper of 6.25cm, and the Cobb value of paper is measured on water imbibition analyzer;
3, it contact angle: takes a fritter to be placed on contact angle instrument on the paper after sizing and measures contact of the water droplet on paper Angle.
As a result as shown in Table 1.
Table one:
Remarks: Cobb value is smaller, illustrates that water-resistance is better, and the contact angle of water droplet and paper is bigger, and the hydrophobicity of paper is better.
As seen from the above table, modified starch base Cypres water-resistance of the present invention is strong and viscosity is high, is worthy to be popularized and uses.

Claims (8)

1. a kind of paper, which is characterized in that it uses following preparation method to be made:
Paper is cut into the scraps of paper of 20cm × 18cm, is layered on level board, then modified starch base Cypres are coated on paper Piece surface, resin added 3g/m2, coating finishes, and is placed in naturally dry at room temperature, and photo drying is close in the sizing face of the scraps of paper Tabula rasa above machine is put into equilibrium water conten in constant-temperature constant-humidity environment after 90s is dried, the paper after sizing is made.
2. modified starch base Cypres according to claim 1, which is characterized in that the modified starch primary surface The specific preparation step of sizing agent are as follows:
(1) 30~40min of impregnation, filtering, isolated filter residue, by institute are vibrated after mixing starch and sodium periodate solution Filter residue and drying is obtained, pretreated starch is obtained;
(2) above-mentioned pretreated starch and water are mixed, is heated to 40~50 DEG C, stirs to get mixed liquor, is adjusted with hydrochloric acid PH of mixed is to 5.5~6.5, then epoxychloropropane is added dropwise into mixed liquor, is heated to 50~60 DEG C, it is stirred to react 3~ 5h obtains crosslinked starch;
(3) it is fitted into reaction kettle after mixing butyl acrylate and above-mentioned crosslinked starch, then potassium peroxydisulfate is added into reaction kettle, 70~80 DEG C, 2~4h of insulation reaction are heated to, sizing agent crude product can be obtained after its cooled to room temperature, it is spare;
(4) rapeseed dregs is weighed, Steam explosion treatment obtains explosion rapeseed dregs, then explosion rapeseed dregs and sodium hydroxide solution are mixed Heating is boiled after conjunction, and filtering removal filter cake, gained filtrate is that mixing cooks liquid;
(5) spare sizing agent crude product and above-mentioned mixing are cooked after liquid mixes and obtains fermentation substrate, fermentation substrate is packed into and is sent out In fermentation tank, then bacillus subtilis bacteria suspension is added into fermentor, is sealed by fermentation;
(6) to it is above-mentioned after fermentation, take out tunning high-temperature sterilization, obtain sterilization fermentation product, then sterilization fermentation is produced Object concentration, gained concentrate is modified starch base Cypres.
3. paper according to claim 1, it is characterised in that: starch as described in step (1) is cornstarch, wheat shallow lake Powder, konjak starch, any one in potato starch;
The mass ratio of starch and sodium periodate solution as described in step (1) is 1:10, and the mass fraction of sodium periodate solution is 10%。
4. paper according to claim 2, it is characterised in that: the quality of pretreated starch and water described in step (2) Than being the 5% of pretreated starch quality for the additional amount of 1:5, epoxychloropropane.
5. paper according to claim 2, it is characterised in that: butyl acrylate and crosslinked starch described in step (3) Mass ratio be 1:2, the additional amount of potassium peroxydisulfate is the 4~5% of crosslinked starch quality.
6. paper according to claim 5, it is characterised in that: the pressure of Steam explosion treatment described in step (4) is 2.0~2.5MPa, time of Steam explosion treatment are 10~15min, and the mass ratio of explosion rapeseed dregs and sodium hydroxide solution is 1:8, the mass fraction of sodium hydroxide solution are 10%, and heating boiling time is 20~30min.
7. paper according to claim 1, it is characterised in that: sizing agent crude product described in step (5) and mixing cook The mass ratio of liquid is 5:1, and the additional amount of bacillus subtilis bacteria suspension is the 5% of fermentation substrate quality, and bacillus subtilis bacterium is outstanding The concentration of liquid is 107cfu/mL, and the temperature of sealing and fermenting is 40~50 DEG C, and the time of sealing and fermenting is 5~7 days.
8. paper according to claim 1, it is characterised in that: high-temperature sterilization temperature described in step (6) be 120~ 130 DEG C, the high-temperature sterilization time is 10~15min, and the concentrate volume after concentration is the 1/3 of sterilization fermentation product original volume.
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