Background technology
A large amount of hydroxyls and small number of carboxylic acid groups are contained in the wood pulp cellulose surface, and these hydroxyls can make fiber disperse better in water, also can the combination by the hydrogen bond force between hydroxyl between the fiber.Coal ash fiber is white or lurid floss, is raw material with flyash, a kind of novel inorganic fibre of making through operations such as high temperature melting, spray silk, coolings.Its main component is SiO
2, Al
2O
3, CaO, Fe
2O
3The surface of fly ash fiber smoother, hydroxy radical content is far smaller than wood pulp cellulose.This directly cause between coal ash fiber self and and wood pulp cellulose between bonding force poor, have influence on the application of coal ash fiber aspect papermaking.So improve the emphasis that is combined into research between coal ash fiber and the wood pulp cellulose.
Chinese patent CN101654891A discloses the new process of production of the efficient paper-making dispersant agent of a kind of acrylic amide, and pure water, yellow soda ash, sodium bicarbonate, tensio-active agent, function monomer, functional agent are modulated.The polymerization of gained modulating liquid is got jel product.Final product is grade packaged through granulation, drying, grinding, branch, required paper-making fibre dispersion agent.This invention is applicable to paper-making fibre and disperses.The gained dispersion agent has that dispersion effect is good, molecular weight is high, good water solubility, non-toxic efficient, advantage such as cheap.
Chinese patent CN101666056A discloses a kind of fly-ash mine fiber paper pulp and preparation technology thereof.Its concrete technology is: with slag, silica and coke mixing granulation on request, burnt material is than being defined as between the 0.12-0.23, with the said mixture high temperature melting, its melt gets rid of silk through whizzer and forms the ore deposit fiber, and the ore deposit fiber dispersion obtains fly-ash mine fiber paper pulp after softening, remove the gred, concentrate, copy the slurry dehydration then.The fine slurry in the ore deposit of this prepared is applicable to papermaking, thereby the alternative or alternative papermaking wood pulp of part is saved the log loss, protects forest resources, and reduces by 20% cost than organic plant fiber papermaking, and manufacture craft is simple, the making processes environmental protection.
Chinese patent CN1580391A discloses a kind of fly ash fiber pulp and has been the papermaking side of raw material.Its technical scheme is: tenderizer 1~10%, dispersion agent 1~8%, surface-modifying agent 1~10%, coal ash fiber 20~80%, organic fibre, water are deployed into flyash paper pulp.The gained paper physical property reaches the equal performance of vegetable fibre paper, is being better than the vegetable fibre paper aspect water tolerance, anti-protection against corrosion and the fire line.This invention can reduce the papermaking cost, gives industrial waste with the functionalization utilization, replaces wood pulp, saves log and expends, and is remarkable to the meaning that protects forest resources.
Above-described invention has certain help for coal ash fiber papermaking, but can not improve the binding ability of coal ash fiber and wood pulp cellulose at all.The present invention seeks to increases the binding ability of coal ash fiber and xylon from both binding abilities of origin solution by adding a kind of properties-correcting agent.The innovative approach of head it off of the present invention is: synthetic a kind ofly be skeleton, introduce the properties-correcting agent of positive ion or cation group on its chain with the water-soluble polymers polyacrylic acid.Surface of fly ash fiber is electronegative, properties-correcting agent with positive charge can be by electrostatic force and coal ash fiber combination, with negative charge can make the modifier molecules chain-unfolding, thereby evenly adhere at fiber surface, institute's synthetic properties-correcting agent has the part amido linkage again, and this part can be by a large amount of hydroxyl combination on hydrogen bond action power and the xylon.And institute's synthetic properties-correcting agent can obtain the different properties-correcting agent of zwitterion proportioning by changing electrochemical conditions, can test motive power the size of the degree influence of keying action is adjusted its zwitterion proportioning, obtains best electric charge ratio.
Summary of the invention
A kind of preparation of polyacrylic acid amide modifier for fly ash fiber paper making and application method, it is characterized in that: at aqueous phase acroleic acid polymerization is become polyacrylic acid earlier, again with N, N-dimethyl-1, the 3-propylene diamine joins and carries out amidation in the polyacrylic acid aqueous solution, the gained amidated products is warming up to 50~80 ℃, and the adding bromination of n-butane carries out quaternized, obtains polyacrylic acid amide modifier.Then, coal ash fiber is dispersed in the water, adds polyacrylic acid amide modifier, stirred 10~15 minutes, interpolation xylon slurry, after mixing, papermaking on the sheet forming machine obtains containing the paper of coal ash fiber.
Described acroleic acid polymerization method is: add earlier the ammonium persulphate of entry, sodium bisulfite, ammonium persulphate gross weight 15%, the vinylformic acid of vinylformic acid gross weight 15% in reactor, the add-on of sodium bisulfite is 2%~8% of a vinylformic acid oven dry weight, reactor is warming up to 70 ℃, remains 85% vinylformic acid then and be made into the aqueous solution and 85% ammonium persulphate and be made into the aqueous solution and be added drop-wise in the reactor simultaneously.Total add-on of ammonium persulphate is 1%~4% of a vinylformic acid oven dry weight, and the dropping time is 2~3 hours.After dropwising, be warming up to 90~92 ℃, be incubated 3 hours, be cooled to below 40 ℃.
Described N, N-dimethyl-1, the add-on of 3-propylene diamine is: vinylformic acid and N, N-dimethyl-1, the molar ratio of 3-propylene diamine are 1: 1~3: 1.
The add-on of described bromination of n-butane is: bromination of n-butane and acrylic acid molar ratio are 1: 1.
Described at coal ash fiber aqueous phase adding polyacrylic acid amide modifier, its add-on is: in the oven dry weight polyacrylic acid amide modifier is 1~10% of coal ash fiber.
Described coal ash fiber and xylon, in dry pulp weight coal ash fiber: wood pulp cellulose is 1: 2.
Embodiment
Embodiment 1
The ammonium persulphate that in the reactor that 250 milliliters of bands stir, heat, adds 80g water, 3g vinylformic acid, 0.4g sodium bisulfite, 0.03g, opening to stir fully dissolves it, reacting by heating still to temperature rises to 70 ℃, again 17g vinylformic acid is made into 50% the aqueous solution, 0.17g ammonium persulphate and is made into 5% the aqueous solution, splash in the reactor simultaneously.The dropping time is 2 hours, is warming up to 90 ℃ then, is incubated 3 hours, is cooled to 40 ℃, obtains the 120.8g polyacrylic acid aqueous solution.In the polyacrylic acid aqueous solution, add N again, N-dimethyl-1,3-propylene diamine 56g carries out amidation, is warming up to 50 ℃, adds bromination of n-butane 38g then, gets polyacrylic acid amide properties-correcting agent 214.8g.
The 9g coal ash fiber is dispersed in the 3000ml water, soaked 20 minutes, add the 0.09g polyacrylic acid amide modifier, stirred 10 minutes, and added the 18g wood pulp cellulose again, stirred 5 minutes, stop to stir, papermaking on the sheet forming machine then obtains containing the paper of coal ash fiber.
Embodiment 2
The ammonium persulphate that in the reactor that 250 milliliters of bands stir, heat, adds 80g water, 3g vinylformic acid, 0.8g sodium bisulfite, 0.06g, opening to stir fully dissolves it, reacting by heating still to temperature rises to 70 ℃, again 17g vinylformic acid is made into 50% the aqueous solution, 0.34g ammonium persulphate and is made into 10% the aqueous solution, splash in the reactor simultaneously.The dropping time is 2 hours, is warming up to 90 ℃ then, is incubated 3 hours, is cooled to 40 ℃, obtains the 212.2g polyacrylic acid aqueous solution.In the polyacrylic acid aqueous solution, add N again, N-dimethyl-1,3-propylene diamine 85g carries out amidation, is warming up to 80 ℃, adds bromination of n-butane 38g then, gets polyacrylic acid amide properties-correcting agent 244.2g.
The 9g coal ash fiber is dispersed in the 3000ml water, soaked 20 minutes, add the 0.9g polyacrylic acid amide modifier, stirred 15 minutes, and added the 18g wood pulp cellulose again, stirred 5 minutes, stop to stir, papermaking on the sheet forming machine then obtains containing the paper of coal ash fiber.
Embodiment 3
The ammonium persulphate that in the reactor that 250 milliliters of bands stir, heat, adds 80g water, 3g vinylformic acid, 1.2g sodium bisulfite, 0.09g, opening to stir fully dissolves it, reacting by heating still to temperature rises to 70 ℃, again 17g vinylformic acid is made into 50% the aqueous solution, 0.51g ammonium persulphate and is made into 10% the aqueous solution, splash in the reactor simultaneously.The dropping time is 2 hours, is warming up to 90 ℃ then, is incubated 3 hours, is cooled to 40 ℃, obtains the 123.3g polyacrylic acid aqueous solution.In the polyacrylic acid aqueous solution, add N again, N-dimethyl-1,3-propylene diamine 28g carries out amidation, is warming up to 70 ℃, adds bromination of n-butane 38g then, gets polyacrylic acid amide properties-correcting agent 189.3g.
The 9g coal ash fiber is dispersed in the 3000ml water, soaked 20 minutes, add the 0.15g polyacrylic acid amide modifier, stirred 12 minutes, and added the 18g wood pulp cellulose again, stirred 5 minutes, stop to stir, papermaking on the sheet forming machine then obtains containing the paper of coal ash fiber.
Embodiment 4
The ammonium persulphate that in the reactor that 250 milliliters of bands stir, heat, adds 80g water, 3g vinylformic acid, 1.6g sodium bisulfite, 0.12g, opening to stir fully dissolves it, reacting by heating still to temperature rises to 70 ℃, again 17g vinylformic acid is made into 50% the aqueous solution, 0.60g ammonium persulphate and is made into 10% the aqueous solution, splash in the reactor simultaneously.The dropping time is 2 hours, is warming up to 90 ℃ then, is incubated 3 hours, cools off 40 ℃, obtains the 124.7g polyacrylic acid aqueous solution.In the polyacrylic acid aqueous solution, add N again, N-dimethyl-1,3-propylene diamine 70g carries out amidation, is warming up to 60 ℃, adds bromination of n-butane 38g then, gets polyacrylic acid amide properties-correcting agent 232.7g.
The 9g coal ash fiber is dispersed in the 3000ml water, soaked 20 minutes, add the 0.6g polyacrylic acid amide modifier, stirred 14 minutes, and added the 18g wood pulp cellulose again, stirred 5 minutes, stop to stir, papermaking on the sheet forming machine then obtains containing the paper of coal ash fiber.
Embodiment 5
The ammonium persulphate that in the reactor that 250 milliliters of bands stir, heat, adds 80g water, 3g vinylformic acid, 0.8g sodium bisulfite, 0.06g, opening to stir fully dissolves it, reacting by heating still to temperature rises to 70 ℃, again 17g vinylformic acid is made into 50% the aqueous solution, 0.34g ammonium persulphate and is made into 10% the aqueous solution, splash in the reactor simultaneously.The dropping time is 2 hours, is warming up to 90 ℃ then, is incubated 3 hours, cools off 40 ℃, obtains the 121.2g polyacrylic acid aqueous solution.In the polyacrylic acid aqueous solution, add N again, N-dimethyl-1,3-propylene diamine 42g carries out amidation, is warming up to 75 ℃, adds bromination of n-butane 38g then, gets polyacrylic acid amide properties-correcting agent 201.2g.
The 9g coal ash fiber is dispersed in the 3000ml water, soaked 20 minutes, add the 0.35g polyacrylic acid amide modifier, stirred 15 minutes, and added the 18g wood pulp cellulose again, stirred 5 minutes, stop to stir, papermaking on the sheet forming machine then obtains containing the paper of coal ash fiber.