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.