CN103459716A - Method for manufacturing paperboard - Google Patents
Method for manufacturing paperboard Download PDFInfo
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- CN103459716A CN103459716A CN2012800175560A CN201280017556A CN103459716A CN 103459716 A CN103459716 A CN 103459716A CN 2012800175560 A CN2012800175560 A CN 2012800175560A CN 201280017556 A CN201280017556 A CN 201280017556A CN 103459716 A CN103459716 A CN 103459716A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H21/00—Non-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
- D21H21/14—Non-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
- D21H21/18—Reinforcing agents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP 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
- D21H21/00—Non-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
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
Abstract
This invention is a method for manufacturing paperboard, the method having an exceptional paper-strength-improving effect and yield-improving effect, and the method being characterized in comprising adding a papermaking additive to a pulp slurry; the pulp slurry being used having a papermaking pH of 6.5-8.5 after the additive has been added; the papermaking additive being synthesized using a monomer (A) capable of forming the repeating unit represented by general formula (A) through polymerization, a cationic vinyl monomer (C) in an amount of 1-20 mol% relative to the total monomer content of the polymerization system, a (meth)allyl sulfonic acid and/or a salt thereof (D) in an amount of 0.01-5 mol% relative to the total monomer content of the polymerization system, and glyoxylic acid or a monomer (B) capable of forming the repeating unit represented by general formula (B) through polymerization; and the papermaking additive containing a polymer having a repeating unit expressed by general formula (B). In the formulae, R1 represents H or CH3, R2 represents H or CH3, and R3 represents H, Na, K, or NH4.
Description
Technical field
The present invention relates to the paperboard manufacture method, especially relate to used (methyl) acrylamide based copolymer paper processed with additive, and stay and the equal excellent paperboard manufacture method of intensity.
Background technology
During paperboard is manufactured, owing to being difficult to obtain high-quality paperboard, so manufactured under acidity.Yet in recent years, because the calcium carbonate composition in the old paper as the paperboard raw material has the tendency of increasing, the PH of copy paper system is difficult to reduce, so because aluminum sulfate or sulfuric acid use amount increase or closure causes sulfate ion increases and the increase of calcium carbonate content, the reactant that causes aluminum sulfate and calcium carbonate is that calcium sulfate (gypsum) increases in the copy paper system, and it separates out and produces fouling (scale troubles) in the copy paper operation.
For addressing these problems, someone has proposed the pulp of employing PH6.5～8.5, basicity 50～400ppm, electrical conductivity 50～250mS/m, and in add jelly and paper power agent and add the paperboard manufacture method (for example can referring to patent documentation 1) that pulp carries out copy paper to.The somebody has proposed such paperboard manufacture method: at the pulp that contains the calcium carbonate more than 5 % by weight, add paper medicine processed, under the condition of PH5～8, wet type is copied in the paperboard manufacture method of system, above-mentioned paper processed adopts the cationic coagulating agent with medicine, paper power reinforcing agent, aluminum sulfate, cementing agent, cationic and is stayed agent and anionic property to stay agent, and the relative adiabatic drying paper pulp of above-mentioned aluminum sulfate addition weight is 0.5～4 % by weight, also at paper processed, use on the interpolation step of medicine, employing is added aluminum sulfate or is added aluminum sulfate and cementing agent (for example can referring to patent documentation 2) simultaneously before adding above-mentioned cementing agent.
Yet, according to the method for above-mentioned proposition, although can solve the problem that produces fouling, due to copy paper PH for neutral, with aluminum sulfate, make paper power reinforcing agent hardly to stay deterioration, can not give full play to the paper power enhancing effect of paper power reinforcing agent.
The problems of the relevant paper quality such as the field trash amount increase in the plain boiled water produced in general papermaking, raw material condition deteriorations, paper machine high speed, paper operation processed also can occurring on the other hand, or copy paper PH change.For addressing these problems, someone has proposed that various paper power strengthens Polyacrylamide resin that containing of effect excellences possess particular configuration additive paper for processed (such as can referring to patent documentation 3).Yet but can't see such record and enlightenment: when the method for this proposition is applicable to copy paper PH, be 6.5～8.5 while but using hardly this non-general paperboard manufacture method of aluminum sulfate, paper power reinforcing agent stay improve, paper power strengthens effect and becomes excellent.In general, copy paper PH6.5～8.5 time hardly with the occasion paper power reinforcing agent of aluminum sulfate stay the paper power of variation, paper power reinforcing agent to strengthen effect can not to give full play to.
The prior art document
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2007-186822 communique
Patent documentation 2: Japanese Patent Laid-Open 2007-154349 communique
Patent documentation 3: Japanese Patent Laid-Open 2000-008293 communique
Summary of the invention
Technical problem
The object of the invention just is to provide a kind of the solution scale problems occurs and descending the paperboard manufacture method of staying with excellent strength in copy paper PH6.5～8.5.
Solution
The inventor is through constantly research with keen determination, finally find to utilize specific paper processed is made an addition to the paperboard manufacture method that pulp, copy paper PH are 6.5～8.5 with additive, not only can solve the generation scale problems and can also accomplish to stay raising effect and paper power to improve the effect excellence, complete the present invention.
That is, the object of the invention is achieved as follows:
<1>a kind of paperboard manufacture method, it is characterized in that, add the i.e. paper additive processed of (methyl) acrylamide based copolymer with structure shown in general formula (B) at pulp, use and add the pulp that in pulp afterwards, copy paper PH is 6.5～8.5; (methyl) allyl sulphonic acid that described (methyl) acrylamide based copolymer is is 0.01～5 % by mole by the cationic vinyl monomer (C) that is at least 1～20 % by mole to the monomer (A) that can form structure shown in general formula (A), the monomer total amount that relatively exists in polymerization system, the monomer total amount that relatively exists in polymerization system and/or its salt (D) carry out polymerization and obtain.
R in formula
1mean H or CH
3
R in formula
2mean H or CH
3, R
3mean H, Na, K or NH
4
<2>a kind of paperboard manufacture method, is characterized in that, at pulp, adds above-mentioned<1>described paper additive processed; About the pulp after adding, by following condition, obtain to stay increase rate (Re) be more than 3%, the copy paper PH of the pulp after interpolation is 6.5～8.5; Use this pulp;
Described condition is:
(i) the pulp temperature of Canadian Standard Freeness being adjusted to the 1 quality % of 300ml is adjusted to 25 ℃;
(ii) take to possess the dynamic quantity of reflux tester (dynamic drainage tester) of 40 order metallic screens, stirred with 600rpm;
(iii) adding relative paper pulp solid content is the paper additive processed of 0.5 quality %;
(iv) add paper processed and start draining with additive after 1 minute, after draining 50g, then draining 150g, then solid content concentration (b) in filtrate is measured;
(v) utilize solid content concentration (a) in the pulp before draining and (iv) in solid content concentration in the filtrate of mensuration, calculating by following formula the rate of staying;
And stay rate (R)=(a-b)/a * 100(%)
(vi) utilize while having added paper processed with additive when staying rate (Rs) and not having interpolation paper processed with additive stay rate (R0), calculating and staying increase rate (Re) by following formula.
And stay increase rate (Re)=(Rs-R0)/R0 * 100(%)
<3>according to above-mentioned<1>or<2>described paperboard manufacture method, it is characterized in that, above-mentioned paper additive processed is (methyl) acrylamide based copolymer with structure shown in general formula (B), and it obtains by monomer is carried out to copolymerization; (methyl) allyl sulphonic acid and/or its salt (D) that the cationic vinyl monomer (C) that the monomer total amount that this monomer contains the monomer (A) that can form structure shown in general formula (A), exist in polymerization system relatively is 1～20 % by mole, the monomer total amount relatively existed in polymerization system are 0.01～5 % by mole and contain the monomer (B) that can form structure shown in general formula (B).
<4>according to above-mentioned<1>to the described paperboard manufacture method of<3>middle any one, it is characterized in that, monomer (A) is (methyl) acrylamide, and monomer (B) is 2-(methyl) acrylamide-N-glycollic acid (2-(meth) acryl amide-N-glycolic acid) class.
<5>according to above-mentioned<1>to the described paperboard manufacture method of<4>middle any one, it is characterized in that, above-mentioned paper additive processed is by making shown in acetaldehyde acids and general formula (A) (methyl) acrylamide based copolymer with structure shown in general formula (B) that structural response forms.
<6>according to above-mentioned<1>to the described paperboard manufacture method of<5>middle any one, it is characterized in that, in the scope that paper additive processed is further also 0.5～10 % by mole in the monomer total amount that polymerization exists in being relatively, used anionic property vinyl monomer (E) to obtain (methyl) acrylamide based copolymer.
<7>according to above-mentioned<6>described paperboard manufacture method, wherein, above-mentioned anionic property vinyl monomer (E) is unsaturated monocarboxylic acid or unsaturated dicarboxylic acid.
<8>described paperboard manufacture method according to above-mentioned<1>～<7>middle any one, it is characterized in that, in the scope that paper additive processed is further also 0.001～2 % by mole in the monomer total amount that polymerization exists in being relatively, used bridging property vinyl monomer (F) to obtain (methyl) acrylamide based copolymer.
<9>described paperboard manufacture method according to above-mentioned<1>～<8>middle any one is characterized in that pulp contains aluminium compound; Relative pulp solid content, the ratio of occupying of aluminium compound is scaled below 0.1 quality % by aluminium oxide.
Effect of the present invention
When existing method is manufactured paperboard, copy paper PH is 6.5～8.5, uses hardly aluminum sulfate, paper power reinforcing agent stay variation, the paper power of paper power reinforcing agent to strengthen effect can not to give full play to.And according to the present invention, can provide can solve occur scale problems and paper power reinforcing agent stay take a turn for the better, paperboard manufacture method that paper power strengthens the effect excellence.
The accompanying drawing explanation
Fig. 1 is dynamic drainage instrument sketch plan.
Concrete embodiment
The present invention is a kind of paperboard manufacture method, it is characterized in that, add the i.e. paper additive processed of (methyl) acrylamide based copolymer with structure shown in general formula (B) at pulp, use and add the pulp that in pulp afterwards, copy paper PH is 6.5～8.5; (methyl) allyl sulphonic acid that described (methyl) acrylamide based copolymer is is 0.01～5 % by mole by the cationic vinyl monomer (C) that is at least 1～20 % by mole to the monomer (A) that can form structure shown in general formula (A), the monomer total amount that relatively exists in polymerization system, the monomer total amount that relatively exists in polymerization system and/or its salt (D) carry out polymerization and obtain.
R in formula
1mean H or CH
3
R in formula
2mean H or CH
3, R
3mean H, Na, K or NH
4
The preferred mode of the present invention is: a kind of paperboard manufacture method, it is characterized in that, and add above-mentioned<1>described paper additive processed at pulp; About the pulp after adding, by following condition, obtain to stay increase rate (Re) be more than 3%, the copy paper PH of the pulp after interpolation is 6.5～8.5; Use this pulp;
Described condition is:
(i) the pulp temperature of Canadian Standard Freeness being adjusted to the 1 quality % of 300ml is adjusted to 25 ℃;
(ii) take to possess the dynamic quantity of reflux tester of 40 order metallic screens, stirred with 600rpm;
(iii) adding relative paper pulp solid content is the paper additive processed of 0.5 quality %;
(iv) add paper processed and start draining with additive after 1 minute, after draining 50g, then draining 150g, then solid content concentration (b) in filtrate is measured;
(v) utilize solid content concentration (a) in the pulp before draining and (iv) in solid content concentration in the filtrate of mensuration, calculating by following formula the rate of staying;
And stay rate (R)=(a-b)/a * 100(%)
(vi) utilize while having added paper processed with additive when staying rate (Rs) and not having interpolation paper processed with additive stay rate (R0), calculating and staying increase rate (Re) by following formula.
And stay increase rate (Re)=(Rs-R0)/R0 * 100(%)
In paperboard manufacture method of the present invention, paperboard can enumerate lining body paper, core raw paper, paper tube base paper, plasterboard body paper, coated white, without coated white, chipboard etc.
Pulp used in the present invention can obtain paper pulp raw material with slurrying such as water for industrial uses.Can use the bleaching such as kraft pulp or sulfite pulp or bleached chemical paper pulps not as paper pulp raw material, the bleaching such as ground wood pulp, mechanical pulp or thermo-mechanical pulp or any one of the old paper paper pulp such as high yield paper pulp bleaching, upper white old paper, old newspaper, outdated magazine, old corrugated paper or the old paper of deinking not.Preferably use old paper paper pulp more than 50%.In addition, can also use the mixture of above-mentioned paper pulp raw material and polyamide, polyester, polyene etc. as above-mentioned paper pulp raw material.Also have, for the main raw material of pulp, filler is arranged, as filler, can enumerate calcium carbonate, carclazyte, talcum powder, chalk, titanium oxide, white carbon etc.
(methyl) added toward pulp with additive as paper processed in the present invention is though the amount of acrylamide based copolymer is not particularly limited, and preferably the pulp solid content adds 0.05～2.0 quality % relatively.The addition of (methyl) acrylamide based copolymer as long as just can realize well the object of the invention in above-mentioned scope, can realized well staying and improve effect and paper power raising effect, but also can not cause the equipment such as paper machine dirty.
In the present invention, preferably toward the relative pulp solid content of pulp, press the aluminium oxide conversion and add the following aluminium compound of 0.1 quality %.Can enumerate aluminum sulfate, polyaluminium chloride, sodium aluminate etc. as aluminium compound.
In addition, effect of the present invention is not being caused in the scope of bad influence, can also add cementing agent, the agent of moistening paper power, pitch control additive, coagulating agent, drainage agent to pulp, stay agent, dyestuff, the needed additive of papermaking such as the agent of sizing mixing, PH adjusting agent.
In the present invention, paper processed is not particularly limited, for example can enumerates mixed stock tank (mixing chest), machine chest (machine chest), header box, fan pump, mesh screen, back flow water pump etc. with the interpolation place of additive.Preferably mixed stock tank, machine chest.
In the present invention, copy paper PH refers to the PH of the pulp before the paper machine dehydration, and copy paper PH is 6.5～8.5.In addition, the pulp PH before the paper machine dehydration, with regard to general actual machine, be equivalent to the PH of entrance.
The present invention's paper additive processed used is (methyl) acrylamide based copolymer with structure shown in general formula (B), should (methyl) acrylamide based copolymer is that (methyl) allyl sulphonic acid that is 0.01～5 % by mole by the cationic vinyl monomer (C) that is at least 1～20 % by mole to the monomer (A) that can form structure shown in general formula (A), the monomer total amount that relatively exists in polymerization system, the monomer total amount that relatively exists in polymerization system and/or its salt (D) carry out polymerization and obtains.
general formula (A)
R in formula
1mean H or CH
3
R in formula
2mean H or CH
3, R
3mean H, Na, K or NH
4
Can enumerate (methyl) acrylamide as the monomer (A) that can form structure shown in general formula (A) used in the present invention.This record of (methyl) acrylamide means to comprise two kinds of acrylamide and Methacrylamides.In the present invention, it is next synthetic that (methyl) acrylamide based copolymer can be used acrylamide and Methacrylamide or one to make monomer (A).
In the present invention, as the monomer (B) that can form structure shown in general formula (B), can enumerate the acrylamide of 2-(methyl) shown in general formula (B1)-N-ethanol acids, for example can enumerate the salt of 2-acrylamide-N-glycollic acid, 2-Methacrylamide-N-glycollic acid or these sodium, potassium, ammonium etc.
R in formula
2mean H or CH
3, R
3mean H, Na, K or NH
4
As need not above-mentioned monomer (B) and the synthetic method with (methyl) acrylamide polymer of structure shown in general formula (B) can exemplify as follows:
(1) make the method for acetaldehyde acids and structural response shown in the general formula (A) formed by polymerization single polymerization monomer (A), cationic vinyl monomer (C) and (methyl) allyl sulphonic acid and/or its salt (D);
(2) make the method for monomer (A), cationic vinyl monomer (C), (methyl) allyl sulphonic acid and/or its salt (D) and the reaction of acetaldehyde acids.
The material that shown in (methyl) acrylamide based copolymer formula of (B) that sometimes will use with additive as paper processed in addition,, structure is done after single body Change calculates is called for short (B) composition.As the acetaldehyde acids, can enumerate the salt of glyoxalic acid and its sodium, potassium, ammonium etc.
As the cationic vinyl monomer (C) that can use in the present invention, for example can exemplify out: (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) acrylic acid dimethylamino propyl ester, (methyl) acrylic acid diethylamino propyl ester, dimethylaminopropyl (methyl) acrylamide or diethylamino propyl group (methyl) acrylamide, cyclopolymers of alkyldiallylamine, dialkyl group allyl amine, diallylamine, allyl amine etc. have the vinyl monomer of tertiary amino, secondary amino group, primary amino radical; Perhaps inorganic acid and even the organic acid salt of these hydrochloric acid, sulfuric acid, formic acid, acetic acid etc.; Perhaps by the vinyl monomer that contains tertiary amino, with quaternizing agents such as the halo aralkyls such as the halogenated alkanes such as chloromethane, bromomethane, benzyl chloride, cylite, dimethyl sulfate, diethyl sulfuric acid, chloropropylene oxide, 3-chlorine-2-hydroxyl oxypropyl trimethyl ammonium chloride, glycidyl tri alkyl ammomium chlorides, react the vinyl monomer that contains quaternary ammonium salt obtained, such as 2-hydroxy-n, N, N, N ', N '-pentamethyl-N '-[3-{ (1-oxygen-2-propenyl) amino } propyl group]-1,3-propane dichloride two ammoniums etc.; The reactant of (methyl) allyl halide and dimethylamino alkylol etc.These can use separately one or more and use.
As (methyl) allyl sulphonic acid (salt) that can use in the present invention (D), can enumerate the alkali metal salts or ammonium salts such as sodium salt, sylvite etc. of allyl sulphonic acid, methallylsulfonic acid and allyl sulphonic acid and methallylsulfonic acid.
As the anionic property vinyl monomer (E) that can use in the present invention, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated tricarboxylic acid, unsaturated quaternary carboxylic acid, unsaturated sulfonic acid, unsaturated phosphonic acids and these salt can be used, a kind of in the middle of these can be used separately or and with two or more.
Can enumerate the alkali metal classes such as acrylic acid, methacrylic acid and these sodium, sylvite or ammonium salt etc. as the unsaturated monocarboxylic acid in the middle of these and its esters.
Can enumerate the alkaline metal salts such as maleic acid, fumaric acid, itaconic acid, citraconic acid and these sodium, sylvite or ammonium salt etc. as unsaturated dicarboxylic acid and the example of its esters.Can enumerate aconitic acid, 3-butene-1 as the example of unsaturated tricarboxylic acid and its esters, 2,3-tricarboxylic acids, 4-amylene-1,2, the alkaline metal salt such as 4-tricarboxylic acids and these sodium, sylvite or ammonium salt etc.
Example as unsaturated quaternary carboxylic acid and its esters can be enumerated 1-amylene-1, Isosorbide-5-Nitrae, 4-tetrabasic carboxylic acid, 4-amylene-1,2,3,4-tetrabasic carboxylic acid and 3-hexene-1,1,6, the alkaline metal salt such as 6-tetrabasic carboxylic acid and these sodium, sylvite or ammonium salt etc.
Can enumerate the alkali metal salts or ammonium salts such as vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamide-2-methyl propane sulfonic and these sodium, sylvite etc. as the example of unsaturated sulfonic acid.
The example of unsaturated phosphonic acids can be enumerated the alkaline metal salts such as vinyl phosphonate, α-phenyl vinyl phosphonic acids and these sodium, sylvite or ammonium salt etc.
In above-mentioned anionic property vinyl monomer, from paper quality, improve effect and Longitude Economic viewpoint, especially preferably unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, be specially acrylic acid, itaconic acid and its esters.
Can exemplify out two (methyl) esters of acrylic acids such as ethylene glycol bisthioglycolate (methyl) acrylate as the bridging property vinyl monomer (F) that can use in the present invention, two (methyl) acrylic amides such as di-2-ethylhexylphosphine oxide (methyl) acrylamide, the divinyl ester classes such as vinyl hexanediacetate, urethane acrylate (urethane acrylate) class, (methyl) allyl acrylate, the diallyl phthalate ester, (methyl) glycidyl acrylate, N replaces (methyl) acrylamide, 1, 3, 5-triacryl six hydrogen-S-triazine (1, 3, 5-triacryloylhexahydro-S-triazine), triallyl isocyanurate, N, N-diallyl acrylamide, the such multi-functional vinyl monomers of 2～4 functionality vinyl monomers such as tetramethylol methane tetraacrylate (tetramethylolmethan tetraacrylate).
Polymerization initiator used in the present invention, be not particularly limited, and can use known.For example can exemplify out: the persulfates such as sodium peroxydisulfate, potassium peroxydisulfate and ammonium persulfate; The peroxide such as hydrogen peroxide, benzoyl peroxide, tert-butyl hydroperoxide and di-tert-butyl peroxide; The bromate such as sodium bromate and potassium bromate; The perborate such as sodium perborate, potassium perborate and ammonium pertorate; The percarbonate such as SODIUM PERCARBONATE, potassium percarbonate and percarbonic acid ammonium; The superphosphates such as peroxophosphoric acid sodium, potassium superphosphate and ammonium superphosphate.Both can be used alone a kind also can and with two or more.Though these polymerization initiators can be used alone, also can as the redox system polymerization initiator, use with the reductant combination.In addition, can also use for example azodiisobutyronitrile, 2 as polymerization initiator, 2 '-azo, two-2-amidine propane hydrochloride, 2,2 '-azo two-2,4-methyl pentane nitrile, 4, the azo-compounds such as 4 '-azo, two-4-cyanopentanoic acid and salt thereof, these both can be used alone a kind also can and with two or more.
And can exemplify out as reductant: sulphite, bisulfites or N, N, N ', N '-organic amines such as tetramethylethylenediamine, 2, the reducing sugars such as azo-compound, aldose such as 2 '-azo, two-2-amidine propane hydrochloride etc.These reductants both can be used alone a kind also can and with two or more.
In addition, can also use as required the known chain-transferring agents such as alkyl hydrosulfide (alkyl mercaptan) class, thioglycolic acid and ester class thereof, isopropyl alcohol, allyl alcohol.
About proportional with containing of structure shown in the contained general formula of (methyl) acrylamide based copolymer (A) of additive as paper processed in the present invention, although be not particularly limited, when preferably structure shown in mutual-through type (A) is done Dan Ti Change calculation, it is 70 % by mole～99 % by mole.Although structure shown in above-mentioned general formula (A) also can realize the object of the invention containing the above-mentioned scope of proportional disengaging, if especially can bring into play paper power raising effect in above-mentioned scope.
About proportional with containing of structure shown in the contained general formula of (methyl) acrylamide based copolymer (B) of additive as paper processed in the present invention, although be not particularly limited, when preferably structure shown in mutual-through type (B) is done Dan Ti Change calculation, it is 0.5～30 % by mole.Although said structure also can realize the object of the invention containing the above-mentioned scope of proportional disengaging, stay if especially can bring into play in above-mentioned scope and improve effect and paper power raising effect.And if surpass 30 % by mole, can not see with cost improve adapt to adhering to of paper pulp improving effect, stay improve effect, paper power improves effect.
In order to obtain using as paper processed in the present invention (methyl) acrylamide based copolymer of additive, the use amount of cationic vinyl monomer (C) monomer is generally 1～20 % by mole, preferably 2～15 % by mole.Also can realize the object of the invention although the use amount of cationic vinyl monomer (C) breaks away from above-mentioned scope, if especially can give full play to paper power in above-mentioned scope, improve effect.
In order to obtain using as paper processed in the present invention (methyl) acrylamide based copolymer of additive, the use amount of (methyl) allyl sulphonic acid and/or its salt (D) is generally 0.01～5 % by mole, preferably 0.05～2 % by mole.Although breaking away from above-mentioned scope, the use amount of (methyl) allyl sulphonic acid and/or its salt (D) also can realize the object of the invention, if but especially make paper processed become easy with the adjustment of additive viscosity in above-mentioned scope, if and surpass higher limit, often can not expect with use amount increase adapt stay and improve effect and strengthen.
In order to obtain using as paper processed in the present invention (methyl) acrylamide based copolymer of additive, the use amount of anionic property vinyl monomer (E) is generally 0.5～10 % by mole, preferably 1～10 % by mole.Also can realize the object of the invention although the use amount of anionic property vinyl monomer (E) breaks away from above-mentioned scope, if especially can bring into play paper processed in above-mentioned scope, by the paper power of additive, improve effect.
In order to obtain using as paper processed in the present invention (methyl) acrylamide based copolymer of additive, the use amount of bridging property vinyl monomer (F) is generally 0.001～2 % by mole, preferably 0.001～1 % by mole.Although breaking away from above-mentioned scope, the use amount of bridging property vinyl monomer (F) also can realize the object of the invention, if easily adjust the viscosity of paper processed with additive in above-mentioned scope.
The manufacture method of (methyl) acrylamide polymer is not particularly limited, and can adopt known the whole bag of tricks in the past.For example, under the inert gas environments such as nitrogen, toward dropping into above-mentioned monomer in the reaction vessel with mixer and thermometer and solvent is water (also can be used together as required organic solvent), also can drop into as required chain-transferring agent, further, can also be as required by these PH adjusting agents of alkali such as the acid such as sulfuric acid, hydrochloric acid or NaOH, potassium hydroxide, ammoniums, modulate PH.Add polymerization initiator, under 20～90 ℃ of reaction temperatures, make to react 1～5 hour, just can access object (methyl) acrylamide based copolymer thereafter.In addition, can also be as required, on one side toward part or all one side polymerization of drip in reaction vessel monomer, water, chain-transferring agent, PH adjusting agent, polymerization initiator.
(methyl) acrylamide based copolymer such as monomer available (A), cationic vinyl monomer (C), (methyl) allyl sulphonic acid and/or its salt (D) and acetaldehyde acids are manufactured.
More specifically, (methyl) acrylamide based copolymer can by following (a) or (b) method obtain:
(a) (methyl) allyl sulphonic acid that the monomer total amount that the cationic vinyl monomer (C) that the monomer total amount that is interior existence by monomer (A), relative polymerization is 1～20 % by mole, relative polymerization are interior existence is 0.01～5 % by mole and/or its salt (D) and acetaldehyde acids drop into same reaction vessel reacts their.
(b) structural response shown in the polymer formula of (A) that (methyl) allyl sulphonic acid that the monomer total amount that allow cationic vinyl monomer (C) that glyoxalic acid is roughly the same 1～20 % by mole by monomer (A), the monomer total amount that relatively exists in polymerization system, relatively has in polymerization system is 0.01～5 % by mole and/or its salt (D) polymerization obtain, import the structure of general formula (B) accordingly.
Reaction condition in above-mentioned two kinds of manufacture methods is not particularly limited, but usually reaction temperature is about 20～90 ℃, 30 minutes～10 hours reaction time.
In the present invention, (methyl) acrylamide based copolymer is normally supplied with the state of the aqueous solution that contains it.Concentration about contained in this aqueous solution (methyl) acrylamide based copolymer is not particularly limited, but considers from cost of transportation, processing mode, preferably 10～40 quality %.About the viscosity of (methyl) acrylamide based copolymer, from pumping liquid, consider, preferably 25 ℃ of lower brookfield viscosity 100～20000mPas.
Molecular weight about (methyl) acrylamide based copolymer, be not particularly limited, but the weight average molecular weight 500,000 that preferably GPC-MALS measures～1,000 ten thousand.When weight average molecular weight is in above-mentioned scope, can bringing into play well to stay and improve effect and paper power raising effect.Too small and less than 500,000 the time when weight average molecular weight, stay, paper power improves poor effect; But, during excessive and 10 million, when adding toward pulp, coagulability is strong sometimes, and paper ground, paper power are brought to harmful effect.
By following condition, obtain stay increase rate, preferably (Re) is the paperboard manufacture method more than 3%.More preferably to stay increase rate (Re) be 3%～20%, further more preferably 5%～15%.And stay increase rate to mean the index through the ratio of the fine paper pulp of twine mesh, and staying increase rate (Re) is 3% when above, can reduce cause through the fine paper pulp of metallic sieve purpose tails off on metallic screen that minute water is poor, the felt hair stops up the problems such as mesh in extrusion process.In addition, dynamic drainage instrument (Dynamic Drainage Jar) is sighted and is used TAPPI T261CM-00(Fine fraction by weight of paper stock by wet screening) that device that provides of the Fig. 1 that puts down in writing.
Described condition is:
(i) the pulp temperature of Canadian Standard Freeness being adjusted to the 1 quality % of 300ml is adjusted to 25 ℃;
The interior bore of (ii) take to possess mixer (3 blade), 40 order metallic screens is the 10.16cm(4 inch) the dynamic drainage instrument, stirred with 600rpm;
(iii) adding relative paper pulp solid content is the paper additive processed of 0.5 quality %;
(iv) add paper processed and start draining with additive after 1 minute, after draining 50g, then draining 150g, then solid content concentration (b) in filtrate is measured;
(v) utilize solid content concentration (a) in the pulp before draining and (iv) in solid content concentration in the filtrate of mensuration, calculating by following formula the rate of staying;
And stay rate (R)=(a-b)/a * 100(%)
(vi) utilize while having added paper processed with additive when staying rate (Rs) and not having interpolation paper processed with additive stay rate (R0), calculating and staying increase rate (Re) by following formula.
And stay increase rate (Re)=(Rs-R0)/R0 * 100(%)
Embodiment
Below according to embodiment, embodiment of the present invention is described, but the present invention is not limited by these embodiment.
Production Example 1
Drop into ion exchange water 610.1g, 50% acrylamide aqueous solution 315.17g, dimethylaminoethyl methacrylate 19.28g, 2-acrylamide-N-glycollic acid 14.22g, 1 in 1 liter of four-hole boiling flask with mixer, thermometer, reflux condensing tube and nitrogen ingress pipe; 3; 5-triacryl six hydrogen-1; 3; 5-triazine (triacrylformal) 0.06g, methallylsulfonic acid sodium 1.97g; then drop into 30% aqueous sulfuric acid 15.93g; get PH3.0, be warmed up to 60 ℃ under nitrogen environment.Then, as polymerization initiator, add 5% ammonium persulfate aqueous solution 5.59g, be warmed up to 90 ℃ under nitrogen environment, insulation.After polymerization starts 1 hour, append and add 5% ammonium persulfate 11.17g, reaction starts to stop polymerization after latter 2 hours.Obtain the aqueous solutions of polymers that contains of solid content 20.1%, viscosity (using the Bu Shi rotation viscometer under 25 ℃) 7500mPas, PH2.9 after cooling.Resulting as shown in table 2 containing the aqueous solutions of polymers proterties.
Production Example 2～8, comparison Production Example 1～3
As shown in table 1, except kind, the mol ratio of (A)～(F) composition changes, carry out the operation same Production Example 1, obtain containing aqueous solutions of polymers.Resulting as shown in table 2 containing the aqueous solutions of polymers proterties.
Production Example 9
Drop into ion exchange water 576.0g, 50% acrylamide aqueous solution 315.23g, dimethylaminoethyl methacrylate 19.28g, 50% glyoxalic acid 14.53g, methallylsulfonic acid sodium 2.33g in 1 liter of four-hole boiling flask with mixer, thermometer, reflux condensing tube and nitrogen ingress pipe, then drop into 30% aqueous sulfuric acid 15.25g, get PH3.0, be warmed up to 60 ℃ under nitrogen environment.Then, as polymerization initiator, add 5% ammonium persulfate aqueous solution 5.59g, be warmed up to 90 ℃ under nitrogen environment, insulation.After polymerization starts 1 hour, append and add 5% ammonium persulfate 11.17g, reaction starts to stop polymerization after latter 2 hours.Obtain the aqueous solutions of polymers that contains of solid content 20.0%, viscosity 6400mPa s, PH2.8 after cooling.Resulting as shown in table 2 containing the aqueous solutions of polymers proterties.
Production Example 10
As shown in table 1, except kind, the mol ratio of (A)～(F) composition changes, carry out the operation same Production Example 9, obtain containing aqueous solutions of polymers.Resulting as shown in table 2 containing the aqueous solutions of polymers proterties.
Table 1
It is as follows that dummy suffix notation in table 1 characterizes the meaning.
AAm: acrylamide
AGA:2-acrylamide-N-glycollic acid
Gly: glyoxalic acid
DM: dimethylaminoethyl methacrylate
DMBz: dimethylaminoethyl methacrylate benzyl chloride quaternary ammonium compound
DABz: acrylic acid dimethylamino ethyl ester benzyl chloride quaternary ammonium compound
IA: itaconic acid
AA: acrylic acid
SMAS: methallylsulfonic acid sodium
TAF:1,3,5-triacryl, six hydrogen-1,3,5-triazines
Table 1 hollow hurdle means not use tie element.
In addition, each becomes in subfield and means its composition kind with above-mentioned dummy suffix notation, and in the record of dummy suffix notation right side is its composition % by mole.Also have, the C composition of Production Example 5 has provided 3 kinds, all with dummy suffix notation, adds and % by mole means and be listed in a line.
Table 2
In Production Example, the mensuration of weight average molecular weight is to utilize in the GPC-MALS method of GPC connection multi-angle light scattering detector to carry out.Condition determination is as follows.
GPC main body: Agilent Technologies (Agilent Technologies) LC1100 series processed
Splitter: the SHODEXSB806MHQ processed of Showa Denko K. K
Leacheate: containing the N/15 phosphate buffer (PH3) of N/10 sodium nitrate
Flow velocity: 1.0ml/ divides
Detector 1: U.S. Wyatt Technology manufactures multi-angle light scattering detector DAWN
Detector 2: the differential refractive index detector RI-101 processed of Showa Denko K. K
About the experiment 1 of staying rate
The past interior bore 10.16cm(4 inch that possesses 40 order metallic screens) dynamic drainage instrument input obtains from old corrugated paper, beating degree (Canadian Standard Freeness) is adjusted into pulps 300ml, pulp density 1.0 quality % (the pulp temperature is 25 ℃) 800g.Now, the stirring rotation number of dynamic drainage instrument (paddle is 3 propeller blades) is set 600rpm for.Pulp drops into after 1 minute 10 seconds, and adding the Production Example 1～10 that is diluted to 0.8 quality % and the resulting paper processed of comparison Production Example 1～3, to make paper processed with additive 5g(be 0.5 quality % with the addition of the relative paper pulp solid content of additive).Add 5g water while in addition, not adding paper processed with additive.Paper processed adds (now pulp PH is 7.5) after 1 minute with additive and opens the plug that dynamic drainage instrument bottom arranges, and discharges 50g filtrate (this filtrate is discarded).Further discharge again 150g filtrate, this filtrate is attracted to filter with Paul Whiteman company (Whatman) No.41 filter paper processed, reclaimed accordingly solid content in filtrate.To the residue on filter paper, under the condition of 105 ℃, 1.5 hours after drying, gravimetry, obtained solid content in filtrate (b) accordingly.Also measure in addition the solid content (a) of the front pulp of discharge opeing, by following formula, calculated the rate (R) of staying.
And stay rate (R)=(a-b)/a * 100(%)
Utilize while adding paper processed with additive stay rate (R0) and added Production Example 1～10 with the resulting paper processed of comparison Production Example 1～3 during with additive stay rate (Rs), calculating and staying increase rate (Re) by following formula.Result is as shown in table 3.
And stay increase rate (Re)=(Rs-R0)/R0 * 100(%)
About the experiment 2 of staying rate
Within 10 seconds, added afterwards that 5g is diluted to the aluminum sulfate of 2.4 quality % and except pulp drops into, to have carried out together about the operation (now pulp PH is 6.2) the experiment 1 of staying rate.Result is as shown in table 3.
Table 3
Embodiment 1
Toward from old corrugated paper, obtain, beating degree (Canadian Standard Freeness) is adjusted into pulps 300ml, pulp density 2.4 quality % and adds aluminum sulfate, making relative paper pulp solid content is 0.5 quality %.Then, be added on Production Example 1～10 and compare the resulting paper additive processed of Production Example 1～3, making relative paper pulp solid content is 0.5 quality %, or does not add, and is stirred.This pulp is after stirring, water dilution with PH7.0, after making pulp density become 0.8 quality % (now the PH of pulp is 7.0), carry out copy paper with The Noble & Wood company handshcet former processed, after extruding with cylindrical drier 100 ℃ of 100 seconds of drying, obtain grammes per square metre 80g/m
2(in breaking factor and paper, ash component is measured and used) and 150g/m
2the handmade paper of (using than the compression strength detection).Resulting paper stock after damping in 24 hours, has carried out various mensuration under 23 ℃, RH50% condition.Do not add paper processed carrying out too with additive.
In addition, the solid content weight ratio that the adding rate of above-mentioned medicine is relative paper pulp adiabatic drying weight.
Measurement result is as shown in table 4.Measuring standard shown in table 4 carries out according to following method.
Breaking factor J I S P8112
Than compression intensity J I S P8126
Ash component .J I S P8128 in paper
Embodiment 2
Except do not add aluminum sulfate (adding rate is 0 quality %), with the water of PH7.5 by pulp density be diluted to 0.8 quality %(now the PH of pulp be 7.5) and, carried out operation the same manner as in Example 1.Measurement result is as shown in table 4.
In the inventive method, preferably pulp contains aluminium compound, and solid content in relative pulp, and the ratio of occupying of aluminium compound is scaled below 0.1 quality % by aluminium oxide.While in pulp, containing aluminium compound, have in the present invention that paper processed brings with additive stay effect and paper power to strengthen effect more to improve this advantage.Can enumerate aluminum sulfate, polyaluminium chloride, sodium aluminate etc. as aluminium compound.
Table 4
Can obviously find out from result shown in table 3 and 4, according to paperboard manufacture method of the present invention, and stay raising, intensity to improve, can think the productivity in the paperboard manufacture, quality raising are had to great role.
Claims (9)
1. a paperboard manufacture method, it is characterized in that, add the i.e. paper additive processed of (methyl) acrylamide based copolymer with structure shown in general formula (B) at pulp, use and add the pulp that in pulp afterwards, copy paper PH is 6.5～8.5; (methyl) allyl sulphonic acid that described (methyl) acrylamide based copolymer is is 0.01～5 % by mole by the cationic vinyl monomer (C) that is at least 1～20 % by mole to the monomer (A) that can form structure shown in general formula (A), the monomer total amount that relatively exists in polymerization system, the monomer total amount that relatively exists in polymerization system and/or its salt (D) carry out polymerization and obtain.
R in formula
1mean H or CH
3
R in formula
2mean H or CH
3, R
3mean H, Na, K or NH
4
2. a paperboard manufacture method, is characterized in that, at pulp, adds the described paper additive processed of claim 1; About the pulp after adding, by following condition, obtain to stay increase rate (Re) be more than 3%, the copy paper PH of the pulp after interpolation is 6.5～8.5; Use this pulp;
Described condition is:
(i) the pulp temperature of Canadian Standard Freeness being adjusted to the 1 quality % of 300ml is adjusted to 25 ℃;
(ii) take to possess the dynamic quantity of reflux tester of 40 order metallic screens, stirred with 600rpm;
(iii) adding relative paper pulp solid content is the paper additive processed of 0.5 quality %;
(iv) add paper processed and start draining with additive after 1 minute, after draining 50g, then draining 150g, then solid content concentration (b) in filtrate is measured;
(v) utilize solid content concentration (a) in the pulp before draining and (iv) in solid content concentration in the filtrate of mensuration, calculating by following formula the rate of staying;
And stay rate (R)=(a-b)/a * 100(%)
(vi) utilize while having added paper processed with additive when staying rate (Rs) and not having interpolation paper processed with additive stay rate (R0), calculating and staying increase rate (Re) by following formula.
And stay increase rate (Re)=(Rs-R0)/R0 * 100(%)
3. paperboard manufacture method according to claim 1 and 2, is characterized in that, above-mentioned paper additive processed is (methyl) acrylamide based copolymer with structure shown in general formula (B), and it obtains by monomer is carried out to copolymerization; (methyl) allyl sulphonic acid and/or its salt (D) that the cationic vinyl monomer (C) that the monomer total amount that this monomer contains the monomer (A) that can form structure shown in general formula (A), exist in polymerization system relatively is 1～20 % by mole, the monomer total amount relatively existed in polymerization system are 0.01～5 % by mole and contain the monomer (B) that can form structure shown in general formula (B).
4. according to the described paperboard manufacture method of any one in claims 1 to 3, it is characterized in that, monomer (A) is (methyl) acrylamide, and monomer (B) is 2-(methyl) acrylamide-N-ethanol acids.
5. according to the described paperboard manufacture method of any one in claim 1 to 4, it is characterized in that, above-mentioned paper additive processed is by making shown in acetaldehyde acids and general formula (A) (methyl) acrylamide based copolymer with structure shown in general formula (B) that structural response forms.
6. according to the described paperboard manufacture method of any one in claim 1 to 5, it is characterized in that, in the scope that paper additive processed is further also 0.5～10 % by mole in the monomer total amount that polymerization exists in being relatively, used anionic property vinyl monomer (E) to obtain (methyl) acrylamide based copolymer.
7. paperboard manufacture method according to claim 6, is characterized in that, above-mentioned anionic property vinyl monomer (E) is unsaturated monocarboxylic acid or unsaturated dicarboxylic acid.
8. according to the described paperboard manufacture method of any one in claim 1 to 7, it is characterized in that, in the scope that paper additive processed is further also 0.001～2 % by mole in the monomer total amount that polymerization exists in being relatively, used bridging property vinyl monomer (F) to obtain (methyl) acrylamide based copolymer.
9. according to the described paperboard manufacture method of any one in claim 1 to 8, it is characterized in that, pulp contains aluminium compound; Relative pulp solid content, the ratio of occupying of aluminium compound is scaled below 0.1 quality % by aluminium oxide.
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| CN114673025B (en) * | 2016-06-01 | 2023-12-05 | 艺康美国股份有限公司 | High-efficiency strength scheme for papermaking in high-charge-demand systems |
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