CN105237648A - Highly-branched starch modified by glyoxal crosslinked polymer, preparation method and application thereof - Google Patents
Highly-branched starch modified by glyoxal crosslinked polymer, preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a highly-branched starch modified by glyoxal crosslinked polymer. The starch comprises highly-branched starch, a polymer (A), which is used to form a polymer carbon skeleton and is prepared through nonionic monomer pre-polymerization, and a polymer (B), which is used to introduce positive charges and is prepared through positive ion pre-polymerization; and the highly-branched starch, the polymer (A) and the polymer (B) carry out crosslinking reactions in the presence of glyoxal so as to generate block copolymerized modified highly-branched starch; wherein the nonionic monomers are selected from acrylamide, N,N-dimethyl acrylamide, N,N-diethyl acrylamide, acrylonitrile, and the like, and the positive ion monomers are selected from dimethyl diallyl ammonium chloride, methyl chloride of dimethyl amino ethyl acrylate and diethyl amino ethyl acrylate, quaternary ammonium salt of benzyl chloride, and the like. The invention also provides an application of the highly-branched starch as a papermaking additive, which can be added into the wet part of a papermaking machine.
Description
Technical field
The present invention relates to a kind of oxalic dialdehyde cross-linked polymer modification high amylopectin starch and its preparation method and application, belong to polymer modification industrial additive and preparation and application technical field thereof.
Background technology
In China's paper industry raw material, due to timber resource shortage, all kinds of recovery paper of a large amount of use is as paper making raw material at present.These raw materials cause fiber short due to the increase of recovered frequency, have a strong impact on the intensity making paper and cardboard, need in paper making process, to add Dry Strength Resin to increase into the intensity index of paper.In the Dry Strength Resin of current use, the Dry Strength Resin of modified starch series almost occupies the market share of the overwhelming majority.All kinds of treated starches such as described in Chinese patent CN102121207A, CN102603977A, CN103015263A and CN103590284A.But the modified starch series Dry Strength Resin of prior art, also exists cost high, limited to raising folding endurance, ring crush intensity, pop strength equal strength index.And paper machine system uses starch as toughener for a long time in a large number, at the bottom of retention, white water system difficulty is caused comparatively greatly to the pollution of the plain boiled water of paper machine.Another shortcoming of the Dry Strength Resin of the modified starch series of prior art causes to paper machine operation, especially on the impact of large high-speed paper motor speed owing to reducing the dehydration rate of wet web while the dry strength increasing paper.
Summary of the invention
The present invention is just for the deficiency that prior art exists, there is provided a kind of oxalic dialdehyde cross-linked polymer modification high amylopectin starch and preparation method thereof, it adds wet end of machine to realize following object as paper making additive: improve the dry strength of Paper or cardboard, bursting strength and folding endurance; Improve the dehydration rate of wet end thus can effectively ensure paper machine operation speed; Improve initial journey retention rate and lower net hole white water consistency to reach.
For solving the problem, the technical solution used in the present invention is as follows:
A kind of oxalic dialdehyde cross-linked polymer modification high amylopectin starch is provided, the polymkeric substance that the polymkeric substance comprising high amylopectin starch and formed for the formation of the non-ionic monomer prepolymerization of macromolecule carbon skeleton and the cationic monomer prepolymerization for introducing positive charge are formed, and the polymkeric substance that the polymkeric substance that formed of described high amylopectin starch, described non-ionic monomer prepolymerization and described cationic monomer prepolymerization are formed carries out by oxalic dialdehyde the modification high amylopectin starch that crosslinking reaction forms block copolymerization;
Described non-ionic monomer be selected from acrylamide, N,N-DMAA, N, N-acrylamide, N-sec.-propyl propylene, N-vinyl formamide, vinyl cyanide one or more;
Described cationic monomer be selected from quaternary ammonium acrylate and methacrylic acid ester quat one or more.Described quaternary ammonium acrylate and methacrylic acid ester quat include but not limited to: dimethylamino ethyl acrylate methyl chloride ammonium salt, dimethylamino ethyl acrylate methylsulfuric acid ammonium salt, dimethylaminoethyl vinylformic acid benzyl chloride ammonium salt, dimethylamino ethyl acrylate vitriol, dimethyl amino ethyl acrylate hydrochloride, dimethylaminoethyl methacrylic ester methyl chloride ammonium salt, dimethylaminoethyl methyl methacrylate ammonium sulfate, dimethylaminoethyl methacrylic acid benzyl chloride ammonium salt, dimethylaminoethyl methacrylic ester vitriol, dimethylaminoethyl methacrylic acid ester hydrochloride, dimethylin acrylamide methviium ammonium sulfate, dimethylin acrylamide hydrochloride, Methacrylamide ammonium chlorine etc.
Specifically preferably, described non-ionic monomer is selected from one or more in acrylamide, N,N-DMAA, N, N-acrylamide, N-vinyl formamide, described cationic monomer is selected from dimethyl diallyl ammonium chloride, the methyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the methyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the methyl chloride quaternary ammonium salt of vinylformic acid Of, the methyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the methyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, the methyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, the benzyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the benzyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the benzyl chloride quaternary ammonium salt of vinylformic acid Of, the benzyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the benzyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, one or more in the benzyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide.
Specifically preferably, the polymericular weight that described non-ionic monomer prepolymerization is formed is 1000 ~ 50000 dalton, the polymericular weight that described cationic monomer prepolymerization is formed is 1000 ~ 50000 dalton, and the molecular weight of described modification high amylopectin starch is 50 ten thousand to 500 ten thousand dalton.
Invention also provides the preparation method of above-mentioned oxalic dialdehyde cross-linked polymer modification high amylopectin starch, comprise the following steps:
Step one, by high amylopectin starch and soft water be in mass ratio (mixing of the ratio of 1 ~ 20) ︰ 100, stirring and dissolving at being warmed up to 100 ~ 160 DEG C, after high amylopectin starch dissolves completely, cools to less than 60 DEG C;
Step 2, in the solution of step one, add polymkeric substance that non-ionic monomer prepolymerization formed, homopolymer that cationic monomer prepolymerization is formed, oxalic dialdehyde and pH buffer reagent; At weak basic condition, carry out crosslinking reaction temperature less than 40 DEG C, in reaction process, in 7.5 ~ 9.5 scopes, control crosslinking reaction speed with the caustic-soda aqueous solution diluted and dilute sulphuric acid adjust ph;
Described pH buffer reagent be selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, sodium hydroxide, potassium hydroxide, strong acid weak base salt, strong base-weak acid salt one or more; Particularly, the consumption of described pH buffer reagent is determined according to actual needs, and the pH value of reaction mixture solution is adjusted between 7.5 ~ 9.5.
Step 3, in the reaction process of step 2, constantly sample viscosimetric, after at 25 DEG C, viscosity reaches 100 ~ 1000mPas, add sulfuric acid adjust ph stopped reaction below 3.0, then add soft water adjustment solid content to 10wt% ~ 20wt%, finally add antiseptic-germicide and namely obtain described oxalic dialdehyde cross-linked polymer modification high amylopectin starch;
Described antiseptic-germicide be selected from anilid class, imidazoles, thiazoles, isothiazolone derivative, quaternary ammonium salt, two croak class, phenols one or more; The consumption of antiseptic-germicide is 0.01% ~ 1% of oxalic dialdehyde cross-linked polymer modification high amylopectin starch total product weight.
Present invention also offers the application of described oxalic dialdehyde cross-linked polymer modification high amylopectin starch as paper making intensifier.
Particularly, described oxalic dialdehyde cross-linked polymer modification high amylopectin starch comprises the following steps as the application method of paper making intensifier: raw material carries out discongesting, pull an oar after, add the aqueous solution of described oxalic dialdehyde cross-linked polymer modification high amylopectin starch, the consumption of described oxalic dialdehyde cross-linked polymer modification high amylopectin starch is 0.2% ~ 0.8% of oven dry stock quality, Paper or cardboard of can manufacturing paper with pulp after fully stirring.
Particularly, described oxalic dialdehyde cross-linked polymer modification high amylopectin starch comprises the following steps as the application method of paper making intensifier: raw material carries out discongesting, pull an oar after manufacture paper with pulp into cardboard, the aqueous solution of described oxalic dialdehyde cross-linked polymer modification high amylopectin starch spray is coated on cardboard, dries.
The ratio of the amylose starch that the starch that different plant generates contains and amylopectin is different, and the amylose starch of some common starch plantses and the content of amylopectin can see the following form 1:
The composition of some common native starches of table 1.
The starch of high branching content of the present invention such as tapioca (flour) and waxy corn starch demonstrate the stability of better strengthening for paper effect and finished product after according to modification preparation of the present invention; Toughener prepared by the present invention is due to the distinctive good dewatering of oxalic dialdehyde cross-linked homopolymer, can the dehydration rate of paper on screen cloth be significantly improved at wet end of machine and improve press part dehydration, its mechanism is: oxalic dialdehyde cross-linked polymer can react with high amylopectin starch and make its Bound moisture become free-water, and then makes press dewatering become easier; Combination simultaneously between fortifying fibre, reduces the rewetting of the rear paper web of squeezing, improves mass dryness fraction; The raising of dehydration rate is the important prerequisite keeping the speed of a motor vehicle, can reduce the problem applying the reduction paper machine speed easily produced in common modifications starch slurry.
Oxalic dialdehyde cross-linked polymer modification high amylopectin starch prepared by the present invention is as toughener, cation group on cationic polymeric molecule chain, amide group etc. can and high amylopectin starch molecule on produce ionic bonding, hydrogen bond and chemical bonds between abundant hydroxyl, stable combination can be formed; After fully mixing with paper pulp after adding wet end of machine, stable electrostatic adhesion, hydrogen bond and chemical bonding can be formed with paper fibre, and on large fiber effective set treated starch adsorb fiber fines, significantly can improve initial journey retention rate and system retention, reach and reduce white water consistency and the effect significantly improving paper performance.
Compared with prior art, implementation result of the present invention is as follows in the present invention:
1, oxalic dialdehyde cross-linked polymer modification high amylopectin starch of the present invention applies the force of cohesion that can significantly improve Paper or cardboard as toughener in slurry, there is significant reinforcing effect to the Paper or cardboard that recovery paper is raw material, have the physical strength such as anti-tensile pulling force, burst index, folding rate of Paper or cardboard and improve significantly.
2, oxalic dialdehyde cross-linked polymer modification high amylopectin starch of the present invention can improve ring crush intensity as toughener significantly in the surface spraying coating of cardboard.
3, oxalic dialdehyde cross-linked polymer modification high amylopectin starch of the present invention not only has raising in essence to the paper product matter of papermaking enterprise as toughener, and the dehydration rate of wet web can be improved, reduce the Bound moisture content of common modifications starch, be conducive to keeping paper machine speed, optimize paper machine operation.
4, oxalic dialdehyde cross-linked polymer modification high amylopectin starch of the present invention also has very large benefiting as toughener to the energy-saving and emission-reduction of papermaking enterprise, can the white-water system of cleaning paper machine, paper plant can be helped better to carry out closed circulation to white-water system, the COD of a large amount of reduction plant effluent and quantity discharged, be conducive to the environmental stress that reduction papermaking enterprise faces.
Embodiment
Below in conjunction with specific embodiments content of the present invention is described.
Specific embodiment 1
The preparation method of a kind of oxalic dialdehyde cross-linked polymer modification high amylopectin starch that the present embodiment provides, main raw material used and charging capacity see table:
| Raw material | Consumption (mass parts) |
| Soft water | 80 parts |
| Tapioca (flour) | 5 parts |
| Prepolymerized polyacrylamide | 10 parts |
| Prepolymerized Poly Dimethyl Diallyl Ammonium Chloride | 1 part |
| Oxalic dialdehyde | 2 parts |
| Ten hydration tetra-na diphosphates | 2 parts |
| Sterilant Kathon CG | 0.1 part |
| Sodium hydroxide | In right amount |
| Sulfuric acid | In right amount |
Preparation method comprises the following steps:
Be equipped with in the 20L reactor of agitator, thermometer, reflux exchanger at one, by 1275g tapioca (flour) and soft water be in mass ratio 6.25 ︰ 100 ratio mixing add, reactor is warming up to 120 DEG C and stirs until tapioca (flour) dissolves completely, then cools to less than 60 DEG C.
Taking out tapioca (flour) solution adds in 2000 ml flasks with turbine agitator, RTD temperature sensor, be 120RPM in agitator stirring velocity, at temperature 40 DEG C, add polyacrylamide homo polymer (molecular weight 10,000 dalton) 135g, Poly Dimethyl Diallyl Ammonium Chloride homopolymer (molecular weight 10,000 dalton) 15g, ten hydration tetra-na diphosphate 30g, oxalic dialdehyde 30g, after stirring by appropriate sodium hydroxide and dilute sulphuric acid adjust ph to 8.5.
After reaching expection viscosity, regulate pH termination reaction with the appropriate vitriol oil, finally adding 1.5g sterilant Kathon CG, to obtain solid content be 20%, and viscosity is 120mPas, and pH value is the oxalic dialdehyde cross-linked homopolymer modification high amylopectin starch of 2.8.
Adopt collection box paperboard (OCC) U.S. useless/state useless (50/50) carries out mixing as raw material, discongest, pull an oar after, add the weight ratio of the oxalic dialdehyde cross-linked homopolymer modification high amylopectin starch aqueous solution 1% ~ 4%(obtained as stated above corresponding to oven dry stock), stir 5 minutes, with the machine-processed write by hand scraps of paper obtaining quantitative 200g/m2 of handsheet, after oven dry, under standard atmosphere condition, balance 24 hours, measure its burst index and folding endurance; The results are shown in table 2.
Table 2. collection box paperboard (OCC) U.S. is useless/intensity index of useless (50/50) the write by hand scraps of paper of state
Specific embodiment 2
The preparation method of a kind of oxalic dialdehyde cross-linked polymer modification high amylopectin starch that the present embodiment provides, main raw material used and charging capacity see table:
Preparation method comprises the following steps:
Be equipped with in the 20L reactor of agitator, thermometer, reflux exchanger at one, by 1275g waxy corn starch and soft water be in mass ratio 6.25 ︰ 100 ratio mixing add, reactor is warming up to 120 DEG C and stirs until waxy corn starch dissolves completely, then cools to less than 60 DEG C.
Taking out waxy corn starch solution adds in 2000 ml flasks with turbine agitator, RTD temperature sensor, be 120RPM in agitator stirring velocity, at temperature 40 DEG C, add polyacrylamide homo polymer (molecular weight 10,000 dalton) 135g, Poly Dimethyl Diallyl Ammonium Chloride homopolymer (molecular weight 10,000 dalton) 15g, ten hydration tetra-na diphosphate 30g, oxalic dialdehyde 30g, after stirring by appropriate sodium hydroxide and dilute sulphuric acid adjust ph to 8.5.
After reaching expection viscosity, regulate pH termination reaction with the appropriate vitriol oil, finally adding 1.5g sterilant Kathon CG, to obtain solid content be 20%, and viscosity is 150mPas, and pH value is the oxalic dialdehyde cross-linked homopolymer modification high amylopectin starch of 2.5.
Adopt collection box paperboard (OCC) U.S. useless/state useless (50/50) carries out mixing as raw material, discongest, pull an oar after, with the machine-processed write by hand scraps of paper obtaining quantitative 200g/m2 of handsheet, the oxalic dialdehyde cross-linked homopolymer modification high amylopectin starch aqueous solution obtained as stated above spray is coated on the write by hand scraps of paper; Consumption is 40 kgs/tonne of paper (weight ratios of toughener/oven dry stock), after oven dry, balances 24 hours, measure its ring crush intensity under standard atmosphere condition; Experimental result lists in table 3.
Beautiful/useless (50/50) the handsheet sheet ring crush intensity index of state of giving up of table 3. collection box paperboard (OCC)
Specific embodiment 3
The monomer of polyacrylamide in specific embodiment 1 is replaced with one or more non-ionic monomers be selected from acrylamide, N,N-DMAA, N, N-acrylamide, N-vinyl formamide, the monomer of Poly Dimethyl Diallyl Ammonium Chloride in specific embodiment 2 is replaced with and is selected from dimethyl diallyl ammonium chloride, the methyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the methyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the methyl chloride quaternary ammonium salt of vinylformic acid Of, the methyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the methyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, the methyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, the benzyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the benzyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the benzyl chloride quaternary ammonium salt of vinylformic acid Of, the benzyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the benzyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, one or more cationic monomers in the benzyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, all the other steps of preparation method are with reference to specific embodiment 1.
With reference to the test method of specific embodiment 1, the obtained oxalic dialdehyde cross-linked polymer modification high amylopectin starch aqueous solution of specific embodiment 3 is as toughener addition when 40kg/ ton oven dry stock, and folding endurance is more than 20, and burst index is more than 2.5kPam2/g.
Specific embodiment 4
The monomer of polyacrylamide in specific embodiment 2 is replaced with one or more non-ionic monomers be selected from acrylamide, N,N-DMAA, N, N-acrylamide, N-vinyl formamide, the monomer of Poly Dimethyl Diallyl Ammonium Chloride in specific embodiment 2 is replaced with and is selected from dimethyl diallyl ammonium chloride, the methyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the methyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the methyl chloride quaternary ammonium salt of vinylformic acid Of, the methyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the methyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, the methyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, the benzyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the benzyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the benzyl chloride quaternary ammonium salt of vinylformic acid Of, the benzyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the benzyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, one or more cationic monomers in the benzyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, all the other steps of preparation method are with reference to specific embodiment 1.
With reference to the test method of specific embodiment 2, the oxalic dialdehyde cross-linked polymer modification high amylopectin starch aqueous solution that specific embodiment 4 obtains is coated on the write by hand scraps of paper as toughener spray, and ring crush intensity is at more than 8.0Nm/g.
Specific embodiment 5
The monomer of polyacrylamide in specific embodiment 1 is replaced with one or more non-ionic monomers be selected from acrylamide, N,N-DMAA, N, N-acrylamide, N-sec.-propyl propylene, N-vinyl formamide, vinyl cyanide;
The monomer of Poly Dimethyl Diallyl Ammonium Chloride in specific embodiment 1 is replaced with one or more cationic monomers be selected from quaternary ammonium acrylate and methacrylic acid ester quat, described quaternary ammonium acrylate and methacrylic acid ester quat include but not limited to: dimethylamino ethyl acrylate methyl chloride ammonium salt, dimethylamino ethyl acrylate methylsulfuric acid ammonium salt, dimethylaminoethyl vinylformic acid benzyl chloride ammonium salt, dimethylamino ethyl acrylate vitriol, dimethyl amino ethyl acrylate hydrochloride, dimethylaminoethyl methacrylic ester methyl chloride ammonium salt, dimethylaminoethyl methyl methacrylate ammonium sulfate, dimethylaminoethyl methacrylic acid benzyl chloride ammonium salt, dimethylaminoethyl methacrylic ester vitriol, dimethylaminoethyl methacrylic acid ester hydrochloride, dimethylin acrylamide methviium ammonium sulfate, dimethylin acrylamide hydrochloride, Methacrylamide ammonium chlorine etc., all the other steps of preparation method are with reference to specific embodiment 1.
With reference to the test method of specific embodiment 1, the obtained oxalic dialdehyde cross-linked polymer modification high amylopectin starch aqueous solution of specific embodiment 5 is as toughener addition when 40kg/ ton oven dry stock, and folding endurance is greater than 15, and burst index is greater than 1.5kPam2/g.
Specific embodiment 6
The monomer of polyacrylamide in specific embodiment 2 is replaced with one or more non-ionic monomers be selected from acrylamide, N,N-DMAA, N, N-acrylamide, N-sec.-propyl propylene, N-vinyl formamide, vinyl cyanide;
The monomer of Poly Dimethyl Diallyl Ammonium Chloride in specific embodiment 2 is replaced with one or more cationic monomers be selected from quaternary ammonium acrylate and methacrylic acid ester quat, described quaternary ammonium acrylate and methacrylic acid ester quat include but not limited to: dimethylamino ethyl acrylate methyl chloride ammonium salt, dimethylamino ethyl acrylate methylsulfuric acid ammonium salt, dimethylaminoethyl vinylformic acid benzyl chloride ammonium salt, dimethylamino ethyl acrylate vitriol, dimethyl amino ethyl acrylate hydrochloride, dimethylaminoethyl methacrylic ester methyl chloride ammonium salt, dimethylaminoethyl methyl methacrylate ammonium sulfate, dimethylaminoethyl methacrylic acid benzyl chloride ammonium salt, dimethylaminoethyl methacrylic ester vitriol, dimethylaminoethyl methacrylic acid ester hydrochloride, dimethylin acrylamide methviium ammonium sulfate, dimethylin acrylamide hydrochloride, Methacrylamide ammonium chlorine etc., all the other steps of preparation method are with reference to specific embodiment 1.
With reference to the test method of specific embodiment 2, the oxalic dialdehyde cross-linked polymer modification high amylopectin starch aqueous solution that specific embodiment 6 obtains is coated on the write by hand scraps of paper as toughener spray, and ring crush intensity is at more than 6.0Nm/g.
Above content is detailed description made for the present invention in conjunction with specific embodiments, can not assert that the present invention specifically implements to be only limitted to these explanations.For those skilled in the art, without departing from the inventive concept of the premise, some simple deduction or replace can also be made, all should be considered as belonging to the scope of protection of the invention.
Claims (7)
1. an oxalic dialdehyde cross-linked polymer modification high amylopectin starch, it is characterized in that, the polymkeric substance that the polymkeric substance comprising high amylopectin starch and formed for the formation of the non-ionic monomer prepolymerization of macromolecule carbon skeleton and the cationic monomer prepolymerization for introducing positive charge are formed, and the polymkeric substance that the polymkeric substance that formed of described high amylopectin starch, described non-ionic monomer prepolymerization and described cationic monomer prepolymerization are formed carries out by oxalic dialdehyde the modification high amylopectin starch that crosslinking reaction forms block copolymerization;
Described non-ionic monomer be selected from acrylamide, N,N-DMAA, N, N-acrylamide, N-sec.-propyl propylene, N-vinyl formamide, vinyl cyanide one or more;
Described cationic monomer be selected from quaternary ammonium acrylate and methacrylic acid ester quat one or more.
2. oxalic dialdehyde cross-linked polymer modification high amylopectin starch as claimed in claim 1, is characterized in that, described non-ionic monomer be selected from acrylamide, N,N-DMAA, N, N-acrylamide, N-vinyl formamide one or more, described cationic monomer is selected from dimethyl diallyl ammonium chloride, the methyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the methyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the methyl chloride quaternary ammonium salt of vinylformic acid Of, the methyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the methyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, the methyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide, the benzyl chloride quaternary ammonium salt of dimethylamino ethyl acrylate, the benzyl chloride quaternary ammonium salt of Dimethylaminoethyl Methacrylate, the benzyl chloride quaternary ammonium salt of vinylformic acid Of, the benzyl chloride quaternary ammonium salt of diethylaminoethyl base ethyl ester, the benzyl chloride quaternary ammonium salt of dimethylamino propyl acrylamide, one or more in the benzyl chloride quaternary ammonium salt of dimethylamino-propyl Methacrylamide.
3. oxalic dialdehyde cross-linked polymer modification high amylopectin starch as claimed in claim 1, it is characterized in that, the polymericular weight that described non-ionic monomer prepolymerization is formed is 1000 ~ 50000 dalton, the polymericular weight that described cationic monomer prepolymerization is formed is 1000 ~ 50000 dalton, and the molecular weight of described modification high amylopectin starch is 50 ten thousand to 500 ten thousand dalton.
4. the preparation method of oxalic dialdehyde cross-linked polymer modification high amylopectin starch as claimed in claim 1, is characterized in that, comprise the following steps:
Step one, by high amylopectin starch and soft water be in mass ratio (mixing of the ratio of 1 ~ 20) ︰ 100, stirring and dissolving at being warmed up to 100 ~ 160 DEG C, after high amylopectin starch dissolves completely, cools to less than 60 DEG C;
Step 2, in the solution of step one, add polymkeric substance that non-ionic monomer prepolymerization formed, homopolymer that cationic monomer prepolymerization is formed, oxalic dialdehyde and pH buffer reagent; At weak basic condition, carry out crosslinking reaction temperature less than 40 DEG C, in reaction process, in 7.5 ~ 9.5 scopes, control crosslinking reaction speed with the caustic-soda aqueous solution diluted and dilute sulphuric acid adjust ph;
Described pH buffer reagent be selected from sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid, sodium hydroxide, potassium hydroxide, strong acid weak base salt, strong base-weak acid salt one or more; Particularly, the consumption of described pH buffer reagent is determined according to actual needs, makes the pH value of reaction mixture solution be adjusted between 7.5 ~ 9.5;
Step 3, in the reaction process of step 2, constantly sample viscosimetric, after at 25 DEG C, viscosity reaches 100 ~ 1000mPas, add sulfuric acid adjust ph stopped reaction below 3.0, then add soft water adjustment solid content to 10wt% ~ 20wt%, finally add antiseptic-germicide and namely obtain described oxalic dialdehyde cross-linked polymer modification high amylopectin starch;
Described antiseptic-germicide be selected from anilid class, imidazoles, thiazoles, isothiazolone derivative, quaternary ammonium salt, two croak class, phenols one or more; The consumption of antiseptic-germicide is 0.01% ~ 1% of oxalic dialdehyde cross-linked polymer modification high amylopectin starch total product weight.
5. oxalic dialdehyde cross-linked polymer modification high amylopectin starch as claimed in claim 1 is as the application of paper making intensifier.
6. oxalic dialdehyde cross-linked polymer modification high amylopectin starch as claimed in claim 5 is as the application of paper making intensifier, it is characterized in that, method comprises the following steps: raw material carries out discongesting, pull an oar after, add the aqueous solution of described oxalic dialdehyde cross-linked polymer modification high amylopectin starch, the consumption of described oxalic dialdehyde cross-linked polymer modification high amylopectin starch is 0.2% ~ 0.8% of oven dry stock quality, Paper or cardboard of can manufacturing paper with pulp after fully stirring.
7. oxalic dialdehyde cross-linked polymer modification high amylopectin starch as claimed in claim 5 is as the application of paper making intensifier, it is characterized in that, method comprises the following steps: raw material carries out discongesting, pull an oar after manufacture paper with pulp into cardboard, the aqueous solution of described oxalic dialdehyde cross-linked polymer modification high amylopectin starch spray is coated on cardboard, dries.
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| CN116587385A (en) * | 2023-06-27 | 2023-08-15 | 广东省林业科学研究院 | Application of glyoxal-acrylamide compound liquid |
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| 张安平等: ""阳离子淀粉-丙烯酰胺接枝共聚物的制备条件对纸张增强效性能的影响"", 《西北轻工业学院学报》 * |
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| CN110730841A (en) * | 2017-06-16 | 2020-01-24 | 凯米拉公司 | Reinforcement system and method for the manufacture of a paper web comprising cellulosic fibers |
| US11242653B2 (en) | 2017-06-16 | 2022-02-08 | Kemira Oyj | Strength additive system and method for manufacturing a web comprising cellulosic fibres |
| CN110730841B (en) * | 2017-06-16 | 2022-05-17 | 凯米拉公司 | Reinforcement system and method for the manufacture of a paper web comprising cellulosic fibers |
| CN116587385A (en) * | 2023-06-27 | 2023-08-15 | 广东省林业科学研究院 | Application of glyoxal-acrylamide compound liquid |
| CN116587385B (en) * | 2023-06-27 | 2024-02-13 | 广东省林业科学研究院 | Application of glyoxal-acrylamide compound liquid |
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| CN105237648B (en) | 2017-08-01 |
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