The content of the invention
The technical problems to be solved by the invention:Film layer embrittlement after being dried for existing natural polymer Cypres
It is easy to crack, surfaces of tacky after making moist, so as to influence the water-resistance of paper and intensity, and easily go mouldy, influence asking for sizing efficiency
Topic, after the present invention carries out oxidation processes first with hydrogen peroxide and ethanol solution to tapioca, add chlorosulfonic acid and ice vinegar
Acid carries out sulfonation processing, modified tapioca starch is obtained, finally using screening and culturing medium to stearothermophilus bud under the conditions of ice-water bath
Spore bacillus carries out screening and culturing, and the strain of acquisition is modified to modified tapioca starch, increases hydrophobicity, and finally addition is natural
Increase antibacterial effect while chitin is as adhesive, so as to which modified starch Cypres be made, prepared by the present invention changes
Property starch surface sizing agent be not easy to go mouldy, and the film layer that is formed is not easy to crack after being coated with and not moisture-sensitive, improves the ring of paper
Oxygen intensity and water repelling property.
In order to solve the above technical problems, the technical solution adopted by the present invention is:
(1)Count in parts by weight, it is 70% ethanol solution, 12 to take 40~50 portions of tapiocas, 60~70 parts of mass fractions
~16 parts of chlorosulfonic acids, 14~19 parts of mass fractions are 15% hydrogen peroxide and 12~15 parts of glacial acetic acid, first successively by above-mentioned weight
Tapioca, the mass fraction of number are 70% ethanol solution and mass fraction is that 15% hydrogen peroxide is put into agitator, temperature
In the four-hole boiling flask of degree meter and dropping funel, and four-hole boiling flask being placed in water-bath, design temperature is 55~60 DEG C, with
300r/min stirs 1~2h;
(2)After above-mentioned stirring terminates, four-hole boiling flask is placed in ice-water bath, then by the chlorosulfonic acid of above-mentioned parts by weight and
Glacial acetic acid is well mixed, and obtains mixed liquor, and is added dropwise to using dropping funel in four-hole boiling flask, control rate of addition for 2 drop/
S, it is stirred with 250r/min, continues 3~6h of stirring after being added dropwise to complete, then take out four-hole boiling flask, use 1.5mol/
Mixture pH is to neutrality in L sodium hydroxide solutions regulation four-hole boiling flask;
(3)Four-hole boiling flask is placed in 1~2h of standing, then be filtered under diminished pressure at room temperature after above-mentioned pH regulations, collects filter
Slag, and the deionized water of 2~3 times of filter residue and its quality is well mixed, then be spray-dried, dried object is collected, obtains modification
Tapioca, it is standby;
(4)Count in parts by weight, take 42~44 portions of sucrose, 32~36 parts of peptones, 26~28 parts of yeast extracts, 7~9 parts
Leucine, 1~2 part of streptomysin, 3~6 parts of petroleum ethers and 2~4 parts of ammonium citrates, stir, and be put into high-temperature sterilization pot
Sterilizing, screening and culturing medium is obtained, by inoculum concentration 10~15%, bacillus stearothermophilus is seeded to screening and culturing medium, and
Screening and culturing medium after inoculation is placed in constant incubator, design temperature is 57~62 DEG C, cultivates 20~24h;
(5)After culture terminates, screening and culturing medium is taken out, screening media surface is eluted using sterilized water, until its
Surface sterile silk, collection leacheate, in mass ratio 1:3~1:5, by leacheate and step(3)Standby modified tapioca starch is put
Enter in container and be well mixed, and container is added into leacheate quality 30 into container after 2~3h of standing under the conditions of 57~62 DEG C
~40% chitin, then container is placed in sterilizing under ultraviolet sterilizing lamp, you can obtain modified starch Cypres.
The application process of the present invention:Fluting medium is laid on glass plate on request first, and one end is fixed
Afterwards, modified starch Cypres prepared by the present invention are spread evenly across on the body paper after fixing, the amount for controlling coating is 25
~35g/m2, after end to be coated, after 3~5min of paper natural air drying after applying glue, then temperature is placed in as 90~105 DEG C of bakings
1~3min is dried in dry machine.
After testing, the film formed after the modified starch Cypres coating that prepared by the present invention is not easy to crack, not moisture-sensitive,
Obtained paper flat crushing strength reaches more than 96N, and side pressure strength reaches more than 765N/m, falls bits amount and is less than 1.025g/m2。
Compared with other method, advantageous effects are the present invention:
(1)The film formed after modified starch Cypres coating prepared by the present invention is not easy to crack, not moisture-sensitive, tear
Index reaches 38.65~41.25mNm2/ g, improve the intensity and water repelling property of paper;
(2)Modified starch Cypres and the adhesion of paper prepared by the present invention are higher, and reduce paper falls bits
Amount, and fall bits amount and be less than 1.025g/m2;
(3)Modified starch Cypres prepared by the present invention are not susceptible to go mouldy, easily storage, and glue applying method is simple, tool
Have broad application prospects.
Embodiment
Count in parts by weight first, it is 70% ethanol solution, 12 to take 40~50 portions of tapiocas, 60~70 parts of mass fractions
~16 parts of chlorosulfonic acids, 14~19 parts of mass fractions are 15% hydrogen peroxide and 12~15 parts of glacial acetic acid, first successively by above-mentioned weight
Tapioca, the mass fraction of number are 70% ethanol solution and mass fraction is that 15% hydrogen peroxide is put into agitator, temperature
In the four-hole boiling flask of degree meter and dropping funel, and four-hole boiling flask being placed in water-bath, design temperature is 55~60 DEG C, with
300r/min stirs 1~2h;After above-mentioned stirring terminates, four-hole boiling flask is placed in ice-water bath, then by above-mentioned parts by weight
Chlorosulfonic acid and glacial acetic acid are well mixed, and obtain mixed liquor, and are added dropwise to using dropping funel in four-hole boiling flask, and speed is added dropwise in control
Spend for 2 drops/s, be stirred with 250r/min, continue 3~6h of stirring after being added dropwise to complete, then take out four-hole boiling flask, make
With mixture pH in 1.5mol/L sodium hydroxide solutions regulation four-hole boiling flask to neutrality;Again by four-hole boiling flask after above-mentioned pH regulations
1~2h of standing at room temperature is placed in, then is filtered under diminished pressure, collects filter residue, and by filter residue and the deionized water of 2~3 times of its quality
It is well mixed, then be spray-dried, dried object is collected, obtains modified tapioca starch, it is standby;Then count in parts by weight, take 42
~44 portions of sucrose, 32~36 parts of peptones, 26~28 parts of yeast extracts, 7~9 parts of leucines, 1~2 part of streptomysin, 3~6 parts of stones
Oily ether and 2~4 parts of ammonium citrates, stir, and are put into sterilizing in high-temperature sterilization pot, screening and culturing medium are obtained, by inoculation
Amount 10~15%, is seeded to screening and culturing medium, and the screening and culturing medium after inoculation is placed in into constant temperature by bacillus stearothermophilus
In incubator, design temperature is 57~62 DEG C, cultivates 20~24h;Finally after culture terminates, screening and culturing medium is taken out, made
Screening media surface is eluted with sterilized water, until its surface sterile silk, collection leacheate, in mass ratio 1:3~1:5, it will drench
Washing lotion is put into container with standby modified tapioca starch and is well mixed, and container is stood into 2~3h under the conditions of 57~62 DEG C
Afterwards, the chitin of leacheate quality 30~40% is added into container, then container is placed in sterilizing under ultraviolet sterilizing lamp,
Modified starch Cypres can be obtained.
Example 1
Count in parts by weight first, it is 70% ethanol solution, 16 parts of chlorine sulphurs to take 50 portions of tapiocas, 70 parts of mass fractions
Acid, 19 parts of mass fractions are 15% hydrogen peroxide and 15 parts of glacial acetic acid, first successively by the tapioca of above-mentioned parts by weight, quality
Fraction is 70% ethanol solution and mass fraction is that 15% hydrogen peroxide is put into four mouthfuls with agitator, thermometer and dropping funel
In flask, and four-hole boiling flask is placed in water-bath, design temperature is 60 DEG C, and 2h is stirred with 300r/min;In above-mentioned stirring knot
Shu Hou, four-hole boiling flask is placed in ice-water bath, then the chlorosulfonic acid of above-mentioned parts by weight and glacial acetic acid are well mixed, must mixed
Liquid, and be added dropwise to using dropping funel in four-hole boiling flask, it is 2 drops/s to control rate of addition, is stirred with 250r/min,
Continue to stir 6h after being added dropwise to complete, then take out four-hole boiling flask, four mouthfuls of burnings are adjusted using 1.5mol/L sodium hydroxide solutions
Mixture pH is to neutrality in bottle;Four-hole boiling flask is placed in after above-mentioned pH regulations again and stands 2h at room temperature, then is filtered under diminished pressure,
Filter residue is collected, and the deionized water of 3 times of filter residue and its quality is well mixed, then is spray-dried, collection dried object, must be changed
Property tapioca, it is standby;Then count in parts by weight, take 44 portions of sucrose, 36 parts of peptones, 28 parts of yeast extracts, 9 parts of bright ammonia
Acid, 2 parts of streptomysins, 6 parts of petroleum ethers and 4 parts of ammonium citrates, stir, and are put into sterilizing in high-temperature sterilization pot, must sieve
Culture medium is selected, by inoculum concentration 15%, bacillus stearothermophilus is seeded to screening and culturing medium, and by the screening and culturing after inoculation
Base is placed in constant incubator, and design temperature is 62 DEG C, cultivates 24h;Finally after culture terminates, screening and culturing medium is taken out,
Screening media surface is eluted using sterilized water, until its surface sterile silk, collection leacheate, in mass ratio 1:5, by leacheate
It is put into container and is well mixed with standby modified tapioca starch, and by container after standing 3h under the conditions of 62 DEG C, into container
The chitin of leacheate quality 40% is added, then container is placed in sterilizing under ultraviolet sterilizing lamp, you can obtains modified starch
Cypres.
Fluting medium is laid on glass plate on request first, and after one end is fixed, prepared by the present invention
Modified starch Cypres are spread evenly across on the body paper after fixing, and the amount for controlling coating is 35g/m2, after end to be coated,
After the paper natural air drying 5min after applying glue, then temperature is placed in dry 3min in 105 DEG C of dryers.After testing, originally
The film formed after modified starch Cypres coating prepared by invention is not easy to crack, and moisture-sensitive, obtained paper concora crush be not strong
Degree reaches 97N, and side pressure strength reaches 767N/m, and it is 1.015g/m to fall bits amount2。
Example 2
Count in parts by weight first, it is 70% ethanol solution, 12 parts of chlorine sulphurs to take 40 portions of tapiocas, 60 parts of mass fractions
Acid, 14 parts of mass fractions are 15% hydrogen peroxide and 12 parts of glacial acetic acid, first successively by the tapioca of above-mentioned parts by weight, quality
Fraction is 70% ethanol solution and mass fraction is that 15% hydrogen peroxide is put into four mouthfuls with agitator, thermometer and dropping funel
In flask, and four-hole boiling flask is placed in water-bath, design temperature is 55 DEG C, and 1h is stirred with 300r/min;In above-mentioned stirring knot
Shu Hou, four-hole boiling flask is placed in ice-water bath, then the chlorosulfonic acid of above-mentioned parts by weight and glacial acetic acid are well mixed, must mixed
Liquid, and be added dropwise to using dropping funel in four-hole boiling flask, it is 2 drops/s to control rate of addition, is stirred with 250r/min,
Continue to stir 3h after being added dropwise to complete, then take out four-hole boiling flask, four mouthfuls of burnings are adjusted using 1.5mol/L sodium hydroxide solutions
Mixture pH is to neutrality in bottle;Four-hole boiling flask is placed in after above-mentioned pH regulations again and stands 1h at room temperature, then is filtered under diminished pressure,
Filter residue is collected, and the deionized water of 2 times of filter residue and its quality is well mixed, then is spray-dried, collection dried object, must be changed
Property tapioca, it is standby;Then count in parts by weight, take 42 portions of sucrose, 32 parts of peptones, 26 parts of yeast extracts, 7 parts of bright ammonia
Acid, 1 part of streptomysin, 3 parts of petroleum ethers and 2 parts of ammonium citrates, stir, and are put into sterilizing in high-temperature sterilization pot, must sieve
Culture medium is selected, by inoculum concentration 10%, bacillus stearothermophilus is seeded to screening and culturing medium, and by the screening and culturing after inoculation
Base is placed in constant incubator, and design temperature is 57 DEG C, cultivates 20h;Finally after culture terminates, screening and culturing medium is taken out,
Screening media surface is eluted using sterilized water, until its surface sterile silk, collection leacheate, in mass ratio 1:3, by leacheate
It is put into container and is well mixed with standby modified tapioca starch, and by container after standing 2h under the conditions of 57 DEG C, into container
The chitin of leacheate quality 30% is added, then container is placed in sterilizing under ultraviolet sterilizing lamp, you can obtains modified starch
Cypres.
Fluting medium is laid on glass plate on request first, and after one end is fixed, prepared by the present invention
Modified starch Cypres are spread evenly across on the body paper after fixing, and the amount for controlling coating is 25g/m2, after end to be coated,
After the paper natural air drying 3min after applying glue, then temperature is placed in dry 1min in 90 DEG C of dryers.After testing, this hair
The film formed after the modified starch Cypres coating of bright preparation is not easy to crack, not moisture-sensitive, obtained paper flat crushing strength
Reach 98N, side pressure strength reaches 768N/m, falls bits amount and is less than 1.022g/m2。
Example 3
Count in parts by weight first, it is 70% ethanol solution, 14 parts of chlorine sulphurs to take 45 portions of tapiocas, 65 parts of mass fractions
Acid, 16 parts of mass fractions are 15% hydrogen peroxide and 13 parts of glacial acetic acid, first successively by the tapioca of above-mentioned parts by weight, quality
Fraction is 70% ethanol solution and mass fraction is that 15% hydrogen peroxide is put into four mouthfuls with agitator, thermometer and dropping funel
In flask, and four-hole boiling flask is placed in water-bath, design temperature is 57 DEG C, and 2h is stirred with 300r/min;In above-mentioned stirring knot
Shu Hou, four-hole boiling flask is placed in ice-water bath, then the chlorosulfonic acid of above-mentioned parts by weight and glacial acetic acid are well mixed, must mixed
Liquid, and be added dropwise to using dropping funel in four-hole boiling flask, it is 2 drops/s to control rate of addition, is stirred with 250r/min,
Continue to stir 5h after being added dropwise to complete, then take out four-hole boiling flask, four mouthfuls of burnings are adjusted using 1.5mol/L sodium hydroxide solutions
Mixture pH is to neutrality in bottle;Four-hole boiling flask is placed in after above-mentioned pH regulations again and stands 2h at room temperature, then is filtered under diminished pressure,
Filter residue is collected, and the deionized water of 2 times of filter residue and its quality is well mixed, then is spray-dried, collection dried object, must be changed
Property tapioca, it is standby;Then count in parts by weight, take 43 portions of sucrose, 33 parts of peptones, 27 parts of yeast extracts, 8 parts of bright ammonia
Acid, 1 part of streptomysin, 5 parts of petroleum ethers and 3 parts of ammonium citrates, stir, and are put into sterilizing in high-temperature sterilization pot, must sieve
Culture medium is selected, by inoculum concentration 12%, bacillus stearothermophilus is seeded to screening and culturing medium, and by the screening and culturing after inoculation
Base is placed in constant incubator, and design temperature is 60 DEG C, cultivates 22h;Finally after culture terminates, screening and culturing medium is taken out,
Screening media surface is eluted using sterilized water, until its surface sterile silk, collection leacheate, in mass ratio 1:4, by leacheate
It is put into container and is well mixed with standby modified tapioca starch, and by container after standing 2h under the conditions of 60 DEG C, into container
The chitin of leacheate quality 35% is added, then container is placed in sterilizing under ultraviolet sterilizing lamp, you can obtains modified starch
Cypres.
Fluting medium is laid on glass plate on request first, and after one end is fixed, prepared by the present invention
Modified starch Cypres are spread evenly across on the body paper after fixing, and the amount for controlling coating is 30g/m2, after end to be coated,
After the paper natural air drying 4min after applying glue, then temperature is placed in dry 2min in 100 DEG C of dryers.After testing, originally
The film formed after modified starch Cypres coating prepared by invention is not easy to crack, and moisture-sensitive, obtained paper concora crush be not strong
Degree reaches 98N, and side pressure strength reaches 779N/m, and it is 1.005g/m to fall bits amount2。