CN105754022A - 3-Vinylamino-2-hydroxypropyltrimethylammonium chloride copolymer and preparation and application thereof - Google Patents
3-Vinylamino-2-hydroxypropyltrimethylammonium chloride copolymer and preparation and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/56—Acrylamide; Methacrylamide
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
- C02F1/56—Macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
-
- 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
- D21H17/45—Nitrogen-containing groups
-
- 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
- D21H19/00—Coated paper; Coating material
- D21H19/36—Coatings with pigments
- D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
- D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
-
- 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
- D21H21/16—Sizing or water-repelling agents
-
- 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
- D21H21/20—Wet strength agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Abstract
The invention discloses 3-vinylamino-2-hydroxypropyltrimethylammonium chloride copolymer and preparation and application thereof.The preparation includes: placing acrylamide monomer and distilled water in a N2 protected reactor, adding a chain transfer agent, a complexing agent and an initiator, stirring at 30-70 DEG C for 10-30 min, standing for 10-30 min, cooling to 10-15 DEG C, adding sodium hydroxide, stirring well and then adding sodium hydrochloride slowly, reacting for 1-3 h, adding sodium hydroxide, reacting for 2-4 h, dropwise adding epichlorohydrin, reacting for 0.1-0.5 h, heating to 50-90 DEG C, reacting for 1-3 h, dropwise adding trimethylamine aqueous solution slowly, and reacting for 2-5 h and then cooling to normal temperature to obtain the 3-vinylamino-2-hydroxypropyltrimethylammonium chloride copolymer; the copolymer is light yellow thick liquid, >/=13% in solid content, 9-10 in pH, 80-100 in degree of polymerization and higher than 60% in amination degree, and is useful as a paper enhancer, a paper sizing agent, a water treating agent and the like.The preparation process is simple, production materials are easy to obtain, a production cycle is short, reacting is mild, and invention is convenient for industrial large-scale production and has a promising application prospect.
Description
Technical field
The invention belongs to fine chemistry industry, environment-friendly material and additive for paper making, water treatment agent field, be specifically related to one
3-ethylene amido-2-Hydroxyproyl Trimethyl ammonia chloride copolymer and preparation thereof and application.
Background technology
Along with the raising of level of consumption, people are more and more higher to the requirement of paper class and quality, how to improve paper
Intensity to meet the demand of people be the direction that people study always.We can improve long stapled proportioning by making beating
With the intensity using reinforcing agent to strengthen paper, wherein, pull an oar and also exist more by long stapled proportioning both approaches
Defect, as big in power consumption, drainability is low, tearability dies down, and paper additive because there are not the problems referred to above and again
Favored by people[1]。
Paper sizing agent can improve the outward appearance of paper and the printability of paper[2], paper strengthening agent can increase paper
Dry, the wet strength opened, rub resistance degree and folding strength etc..Paper strength by between intensity and the fiber of pulp fiber self or
Bond strength between coating, the impact of area etc. is relatively big, and the combination of paper pulp fiber is the main cause that paper strength increases, and
Sizing agent is to give paper hydrophobicity and resist fluids permeability by its hydrophilic, hydrophobic property group, and reinforcing agent is through it and contains
The copolymer of specific groups makes to form hydrogen bond between cellulosic molecule thus improves intensity and the properties of paper[3].When
Before, the use to wet strength agent is all proximate to net front interpolation, is on the one hand due to its high-cation, required for the absorption of fiber
Time short, it is to avoid stop for a long time, attached by the anion back suction in water, reduce slurry Zeta potential；On the other hand, reduce
The equipment such as the streaming shear action to wet strength agent polymer segment, reduces wet potent fruit[4]。
Recently as coated broke, deinked waste paper, the use of high yield pulp so that the interfering anion of wet end of machine
The aggregate concentration of impurity is more and more higher, and instrument can cause certain injury.And traditional cation sizing agent generally uses starch, but
It is that fiber molecule horizontal integration area is improved limited by general starch based paper making intensifier, and expends a large amount of grain, economic benefit
Poor[5].Conventional size agent emulsion use cationic starch is as emulsifying agent and stabilizer, but such emulsion staying on fiber
Rate ratio relatively low, compare with fiber-reactive slowly, the required applying glue time is long[6]。
In order to preferably solve anionic impurity, applying glue is brought series of problems, it would be desirable to seek a kind of charge density
Higher polymer replaces cationic starch.Under the trend of neutual-alkaline papermaking technology, response type neutral-to-alkaline sizing agents
Having sizing efficiency high, the features such as applying glue consumption is few are allowed to be widely used in paper industry[7]。
Polyvinylamine is the straight chain cation water-soluble high molecular polymer that a kind of amino is connected directly between on hydrocarbon backbone,
Containing a lot of side functional group amino, can react with aldehydes, anhydrides, carboxylic acids, halogenated hydrocarbons etc., moreover it is possible to carry out network with metal ion
Closing, prepare other functional macromolecule materials, it can improve the wet strength of paper as environmentally friendly wet strength agent, to containing
Filler and fiber fines have cementation, also function to good retention aid and filtering aid effect, and its molecular chain length and charge density also can roots
It is adjusted according to practical application request, therefore has the most wide application prospect[8]。
Tanaka[9,10,11]Having prepared aminating degree under cryogenic with polyacrylamide and substantial amounts of sodium hydroxide is 96%
Polyvinylamine, research find, amide groups has once carried out N-chloroamides, is the most no longer converted into carboxylic acid group, suitably
Control the concentration of sodium hypochlorite, the hydrolysis of amide can be suppressed in the lowest level, thus prepare the product of certain aminating degree
Thing；Achari[12]Et al. Hofmann reaction synthesizing polyethylene amine has been carried out numerous studies, during he thinks and exists in course of reaction
Between the side reaction such as the cyclization of product, the hydrolysis of raw material amide group, main chain chain rupture, but when the molecular mass of raw material is less, hypochlorous acid
When the mol ratio of sodium and amide group is less than 1, the side reaction in course of reaction can effectively be contained.Zhang Zhenqian etc.
People[13]Studies have shown that the Hofmann reaction with cross-linked polyacrylamide as raw material, the degree of polymerization is low for improving raw material
Polyacrylamide degradation rate is favourable, and sums up the optimal conditions of synthesizing cross-linked polyvinylamine.
Wherein, hoffman degradation reaction formula is as follows:
Chen Fushan[14]Et al. have studied the polyvinylamine potentiation to paper industry, test result indicate that, PVAm is at various ph values
Charge density different, the charge density of acid condition is higher than alkalescence condition.As reinforcing agent, the aminating degree of PVAm is the highest, increases
Potent fruit is the best.When system pH value is 4 ~ 9, add 0.2% consumption, aminating degree be 30% ~ 50% PVAm to bleaching leaf wood
Slurry has significant potentiation with bleaching needle-point leaf pulp mixing slurry.Xu Guihong[15]Et al. be prepared for high solids content PPE papermaking
Wet strength agent also have studied its stability, and result shows when Substance is 80g/m2, self-control high solids content PPE wet strength agent adds
When amount is 0.875% (dry solids is relative to oven dry stock), wet strength is the highest, has reached about 26.5%, and the stable storing of product
Property is preferable.Qiu Qingyuan et al.[16]The potato starch acrylamnide graft copolymerization caused with cerium redox system and product thereof are made
The applied research of papery reinforcing agent.Peng Tianxing[17]Utilizing polyvinylamine to process waste paper deinking waste water, result shows poly-second
Enamine has good decolouring and goes turbid performance. and have superiority in terms of processing the waste water that negative charge amount is higher.Sun Weimin et al.[18]
By cationic organic high-molecular modification is studied, the side chain of polymeric amine can be carried out Mannich reaction, quaternized instead
Should so that it is with dissociable cation group, it is more suitable for water and processes utilization.
Instant invention overcomes conventional size agent makes the fiber in slurry, filler etc. that the problems such as poly-, the precipitation of wadding to occur, and reduces system
Unnecessary loss during Bei, and while ensureing that sizing efficiency is excellent, paper-making process auxiliary agent is not produced ill effect.
List of references:
[1] Beijing Forestry University. cationic sheet paper reinforcing agent and production thereof and using method: China,
CN201210306185. X[P]. 2013-1-2.
[2] Liang H, Long Z, Yang S, et al. Organic modification of bentonite and
its effect on rheological properties of paper coating[J]. Applied Clay
Science, 2015, 104: 106-109.
[3] Zhu Zhongxiang, executes Herba Cymbidii Goeringii, remaining loyalty forever etc. the application [J] that polyvinylamine produces at Cultural Paper. and China's paper industry,
2013, (21): 25-28.
[4] Liu Wen. wet strength agent is on making beating and the impact [J] of paper performance thereof. Paper Science & Technology, 2015 (4):
61-63.
[5] Wang Songlin, Hu Huiren, Guo Shuhua etc. the applying glue serviceability of Maninot esculenta crantz. and maize oxidized starch compares [J]. paper
And papermaking, 2008,27 (z1): 49-50.
[6] Tianjin University of Commerce. the preparation method of a kind of composite surface sizing agent: China, CN201310728623. 6
[P]. 2014-4-2.
[7] king builds, Zhou Xiaowei, Lian Anfeng etc. and polyvinylamine substitutes cationic starch and makees the research [J] of paper making intensifier.
China's paper industry, 2010,31 (16): 36-38.
[8] Kanie O, Tanaka H, Mayumi A, et al. Composite sheets with
biodegradable polymers and paper, the effect of paper strengthening agents on
strength enhancement, and an evaluation of biodegradability[J]. Journal of
applied polymer science, 2005, 96(3): 861-866.
[9] Tanak H, Senju R. Preparation of polyvinylamine by Hofmann
degradation of polyacrylamide [J]. Bull. Chem. Soc. Jpn., 1976, 49(10): 2821-
2823.
[10] Tanak H. Hofmann reaction of polyacrylamide; relationship between
reaction condition and degree of polymeriza tion of polyvinylamine[J]. J.
Polym. Sci.: Polym. Chem. , 1979, 17: 1239-1245.
[11] Tanaka H.Cationic modification of ultrahigh molecular-weight
polyacrylamide by the Hofmann degradation[J]. Journal of Polymer Science:
Polymer Lerrers Edition, 1978, 16: 87-89.
[12] Achari A,Coqueret X,Lablache-Combier A,etal. Preparation of
polyvinylamine from polyacrylamide: a reinvestigation of the Hofmann reaction
[J]. Macromol. Chem. Phy., 1993, 194: 1879-1891.
[13] Zhang Zhenqian, Lu Jianmei, Wang Lihua etc. the synthesis of cross-linked polyvinylamine and performance study [J]. petrochemical industry,
2002, 31(4): 254-258.
[14] Chen Fushan, Guo Zhen, Wang Lijun etc. the preparation of polyvinylamine and as the research [J] of paper making intensifier.
China's papermaking, 2007,26 (4): 27-30.
[15] king's root, Wang Wei, Hu Haitao etc. the application [J] in cultural paper produces of the polyvinylamine filling modifier.
China's papermaking, 2013,32 (9): 11-14.
[16] Qiu Qingyuan, Zhang Chaoling, yellow Xiao Ming, Yang Liping etc. the starch acrylamide acyl caused with cerium redox system
Amine graft copolymerization and product thereof make the applied research [J] of papery reinforcing agent. southwest papermaking, and 1989, (the 4th phase).
[17] Peng Tianxing, Lin Mei, old few equality. polyvinylamine is decoloured in waste paper deinking waste water and is gone turbid performance study [J].
Fujian chemical industry, 2003, (3): 23-24,12.
[18] Sun Weimin, Zhang Guangcheng, Zhao Qing recognize. the progress [J] of cationic organic high-molecular water treatment agent. and material
Material exploitation and application, 2012,27 (2): 112-118.
Summary of the invention
It is an object of the invention to provide a kind of 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer and preparation thereof
Methods and applications.This copolymer can strengthen the tensile index of paper, resistance to broken coefficient and tear index as paper strengthening agent；Make
Paper break length, folding strength and machine washable degree etc. can be increased for paper sizing agent；The colourity of waste water can be removed as flocculant,
Reduce CODCrValue.Preparation technology is easy, working condition is less demanding, equipment needed thereby is conventional equipment.Preparation technology of the present invention letter
Just, working condition is less demanding, equipment needed thereby is conventional equipment.
For achieving the above object, the present invention adopts the following technical scheme that
The preparation method of a kind of 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer, by acrylamide monomer and distillation
Water puts into N2In the reactor of protection, add chain-transferring agent, chelating agent and initiator, after stirring reaction, add sodium hydroxide,
Sodium hypochlorite, sodium hydroxide, epoxychloropropane and trimethylamine aqueous solution, prepare 3-ethylene amido-2-Hydroxyproyl Trimethyl chlorine
Change amine copolymer thing.
In more detail, acrylamide monomer and distilled water are put into N2In the reactor of protection, add chain-transferring agent, complexation
Agent and initiator, 30 ~ 70 DEG C of stirring 10 ~ 30 min, it is cooled to-10 ~ 15 DEG C after standing 10 ~ 30 min, adds sodium hydroxide,
It is slowly added to sodium hypochlorite after stirring, adds sodium hydroxide reaction 2 ~ 4 h after reaction 1 ~ 3 h, drip epoxychloropropane,
It is warming up to 50 ~ 90 DEG C after reaction 0.1 ~ 1.5 h, is slowly added dropwise trimethylamine aqueous solution after reaction 1 ~ 3 h, cools down after reaction 2 ~ 5 h
To room temperature, obtain 3-ethylene amido-2-Hydroxyproyl Trimethyl ammonia chloride copolymer.
Raw material is calculated by weight as:
Acrylamide monomer: 2.0 parts ~ 4.0 parts,
Initiator: 0.05 part ~ 0.2 part,
Chelating agent: 0.1 part ~ 0.5 part,
Chain-transferring agent: 0.1 part ~ 1.0 parts,
Sodium hydroxide: 10.0 parts ~ 20.0 parts,
Sodium hypochlorite (10 wt%): 15.0 parts ~ 25.0 parts,
Epoxychloropropane: 0.2 part ~ 1.0 parts,
Trimethylamine: 0.2 part ~ 1.0 parts,
Distilled water: 40.0 parts ~ 70.0 parts.
The initiator of above-mentioned technique is Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate .-sodium sulfite or over cure
The mixture of one or more in acid sodium-sodium sulfite.
The chelating agent of above-mentioned technique is disodiumedetate (EDTA2Na), acetylacetone,2,4-pentanedione, sodium pyrophosphate, amino three
The mixture of one or more in acetic acid, hydroxyethylethylene diamine tri-acetic acid (HEDTA) or bicine N-(DEG).
The chain-transferring agent of above-mentioned technique is in carbamide, isopropanol, sodium formate, aliphatic mercaptan or lauryl mercaptan
Kind or several mixture.
Obtained copolymer is light yellow viscous liquid, solid content >=13%, pH value: 9 ~ 10, the degree of polymerization 80 ~ 100, amine
Change degree is more than 60%.
A kind of 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer as above is at paper strengthening agent, paper
Application in sizing agent or water treatment agent.
The reaction equation of the present invention is as follows:
。
Compared with prior art, present invention have the advantage that
1, in the present invention preparation 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer, as plasm-glue-blending, can in
Property paste system in use and play a role, wadding is poly-, precipitation not to make the fiber in slurry, filler etc. occur；The most on stream
Tube wall, pool wall, cylinder mould, fourdrinier wire etc. produce stickum, are difficult to cause the bacterial reproduction in paste system；Paper-making process is not added
Auxiliary agent produces ill effect；Sheet forming performance is not produced harmful effect；Add glue system as top sizing not produce
Wadding is poly-, precipitation, the viscosity of inconspicuous increase surface size and viscosity, not the pool wall in surface sizing system, tube wall, various
Roll surface of roller etc. gum deposit block, glue dirt；
2, the 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer of preparation in the present invention, can improve fiber fines, filler
Retention, improve copy paper system clean degree, reduce waste water CODCr；
3, the 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer of preparation in the present invention, can as paper strengthening agent
Strengthen the tensile index of paper, resistance to broken coefficient and tear index；
4, the 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer of preparation in the present invention, can be effective as flocculant
Remove the float in water and colloidal substance, reduce the COD in waterCrValue, strong adaptability, good decolorizing effect, can be widely used in
The industries such as paper waste, light textile, printing and dyeing；
5, this product preparation process is simple, and raw materials for production are easy to get, with short production cycle, reaction gentleness, and equipment needed thereby is conventional equipment,
It is convenient for industrialized great production.
Detailed description of the invention
Present invention process is as follows:
2.0 parts ~ 4.0 parts acrylamide monomers and distilled water are put into N2In the reactor of protection, add 0.1 part ~ 1.0 parts chains and turn
Move agent, 0.1 part ~ 0.5 part chelating agent and 0.05 part ~ 0.2 part initiator, 30 ~ 70 DEG C of stirring 10 ~ 30 min, stand 10 ~ 30
It is cooled to-10 ~ 15 DEG C after min, adds 2.0 parts of sodium hydroxide, after stirring, be slowly added to 10.0 parts ~ 20.0 parts hypochlorous acid
Sodium, adds 8.0 parts ~ 18.0 parts sodium hydroxide reaction 2 ~ 4 h, drips 0.2 part ~ 1.0 parts epoxychloropropane after reaction 1 ~ 3 h,
It is warming up to 50 ~ 90 DEG C after reaction 0.1 ~ 1.5 h, is slowly added dropwise 0.2 part ~ 1.0 parts trimethylamine aqueous solutions after reaction 1 ~ 3 h, reaction
It is cooled to room temperature after 2 ~ 5 h, obtains 3-ethylene amido-2-Hydroxyproyl Trimethyl ammonia chloride copolymer.
Raw material is calculated by weight as:
Acrylamide monomer: 2.0 parts ~ 4.0 parts,
Initiator: 0.05 part ~ 0.2 part,
Chelating agent: 0.1 part ~ 0.5 part,
Chain-transferring agent: 0.1 part ~ 1.0 parts,
Sodium hydroxide: 10.0 parts ~ 20.0 parts,
Sodium hypochlorite (10%): 15.0 parts ~ 25.0 parts,
Epoxychloropropane: 0.2 part ~ 1.0 parts,
Trimethylamine: 0.2 part ~ 1.0 parts,
Distilled water: 40.0 parts ~ 70.0 parts；
Following example added medicine summation is 1000 kilograms.
Wherein, sodium hydroxide distilled water adds after being formulated as 30wt% ~ 40wt% solution, and trimethylamine is also to use distilled water
Add after being configured to aqueous solution.
Embodiment 1
1. raw material group used by the present embodiment following (unit: kilogram)
Acrylamide monomer: 22.0 kilograms,
Chain-transferring agent (carbamide): 5.0 kilograms,
Chelating agent (EDTA2Na): 2.0 kilograms,
Initiator (Ammonium persulfate. and potassium peroxydisulfate mixture, quality proportioning is 1:1): 2.0 kilograms,
Sodium hydroxide: 121.0 kilograms,
Sodium hypochlorite (10%): 250.0 kilograms,
Epoxychloropropane: 5.0 kilograms,
Trimethylamine: 3.0 kilograms,
Distilled water: 590.0 kilograms；
2. step of preparation process and parameter
(1) being dissolved in by acrylamide monomer in 215.0 kilograms of distilled water, and add chain-transferring agent, chelating agent, initiator, 40
Stir 15 minutes under DEG C water bath condition, stand 20 minutes；
(2) under the conditions of 10 DEG C, stir and add 12.0 kilogram sodium hydroxide, be allowed to mix homogeneously, be slow added into
Sodium hypochlorite, stirring reaction 2 hours, add 109.0 kilogram sodium hydroxide, stirring reaction 2 hours；
(3) under the conditions of 20 DEG C, epoxychloropropane is dripped, stirring reaction 0.4h, it is warming up to 70 DEG C, is slowly added dropwise trimethylamine water-soluble
Liquid, reacts 2 hours, is cooled to room temperature.
Embodiment 2
1. raw material group used by the present embodiment following (unit: kilogram)
Acrylamide monomer: 22.0 kilograms,
Chain-transferring agent (carbamide): 5.0 kilograms,
Chelating agent (EDTA2Na): 2.0 kilograms,
Initiator (Ammonium persulfate .): 1.0 kilograms,
Sodium hydroxide: 121.0 kilograms,
Sodium hypochlorite (10%): 224.0 kilograms,
Epoxychloropropane: 6.0 kilograms,
Trimethylamine: 4.0 kilograms,
Distilled water: 615.0 kilograms；
2. step of preparation process and parameter
(1) being dissolved in by acrylamide monomer in 215.0 kilograms of distilled water, and add chain-transferring agent, chelating agent, initiator, 40
Stir 15 minutes under DEG C water bath condition, stand 20 minutes；
(2) under the conditions of 5 DEG C, stir and add 12.0 kilogram sodium hydroxide, be allowed to mix homogeneously, be slow added into secondary
Sodium chlorate, stirring reaction 2 hours, add 109.0 kilogram sodium hydroxide, stirring reaction 4 hours.
(3) under the conditions of 30 DEG C, epoxychloropropane is dripped, stirring reaction 0.3h, it is warming up to 70 DEG C, is slowly added dropwise trimethylamine
Aqueous solution, reacts 2 hours, is cooled to room temperature.
Embodiment 3
1. raw material group used by the present embodiment following (unit: kilogram)
Acrylamide monomer: 22.0 kilograms,
Chain-transferring agent (carbamide and isopropanol mixture, quality proportioning is 1:1): 5.0 kilograms,
Chelating agent (EDTA2Na Yu HEDTA mixture, quality proportioning is 1:1): 2.0 kilograms,
Initiator (Ammonium persulfate. and potassium peroxydisulfate mixture, quality proportioning is 1:1): 3.0 kilograms,
Sodium hydroxide: 150.0 kilograms,
Sodium hypochlorite (10%): 200.0 kilograms,
Epoxychloropropane: 6.0 kilograms,
Trimethylamine: 4.0 kilograms,
Distilled water: 608.0 kilograms；
2. step of preparation process and parameter
(1) being dissolved in by acrylamide monomer in 180.0 kilograms of distilled water, and add chain-transferring agent, chelating agent, initiator, 40
Stir 15 minutes under DEG C water bath condition, stand 20 minutes；
(2) under the conditions of 15 DEG C, stir and add 20.0 kilogram sodium hydroxide, be allowed to mix homogeneously, be slow added into
Sodium hypochlorite, stirring reaction 2 hours, add 130.0 kilogram sodium hydroxide, stirring reaction 4 hours；
(3) under the conditions of 15 DEG C, epoxychloropropane is dripped, stirring reaction 0.2h, it is warming up to 70 DEG C, is slowly added dropwise trimethylamine water-soluble
Liquid, reacts 2 hours, is cooled to room temperature.
Embodiment 4
1. raw material group used by the present embodiment following (unit: kilogram)
Acrylamide monomer: 30.0 kilograms,
Chain-transferring agent (carbamide and isopropanol mixture, quality proportioning is 1:1): 5.0 kilograms,
Chelating agent (EDTA2Na Yu HEDTA mixture, quality proportioning is 1:1): 3.0 kilograms,
Initiator (Ammonium persulfate. and sodium peroxydisulfate-sodium sulfite mixture, quality proportioning is 1:1): 1.5 kilograms,
Sodium hydroxide: 120.0 kilograms,
Sodium hypochlorite (10%): 250.0 kilograms,
Epoxychloropropane: 6.5 kilograms,
Trimethylamine: 5.0 kilograms,
Distilled water: 579.0 kilograms；
2. step of preparation process and parameter
(1) being dissolved in by acrylamide monomer in 250.0 kilograms of distilled water, and add chain-transferring agent, chelating agent, initiator, 50
Stir 15 minutes under DEG C water bath condition, stand 30 minutes；
(2) under the conditions of 15 DEG C, stir and add 12.0 kilogram sodium hydroxide, be allowed to mix homogeneously, be slow added into
Sodium hypochlorite, stirring reaction 2 hours, add 108.0 kilogram sodium hydroxide, stirring reaction 4 hours；
(3) under the conditions of 15 DEG C, epoxychloropropane is dripped, stirring reaction 0.2h, it is warming up to 75 DEG C, is slowly added dropwise trimethylamine water-soluble
Liquid, reacts 3 hours, is cooled to room temperature.
Embodiment 5
1. raw material group used by the present embodiment following (unit: kilogram)
Acrylamide monomer: 22.0 kilograms,
Chain-transferring agent (carbamide and sodium formate mixture, quality proportioning is 1:1): 7.5 kilograms,
Chelating agent (EDTA2Na Yu DEG mixture, quality proportioning is 1:1): 2.0 kilograms,
Initiator (sodium peroxydisulfate and potassium peroxydisulfate mixture, quality proportioning is 1:1): 1.0 kilograms,
Sodium hydroxide: 121.0 kilograms,
Sodium hypochlorite (10%): 224.0 kilograms,
Epoxychloropropane: 6.0 kilograms,
Trimethylamine: 4.0 kilograms,
Distilled water: 612.5 kilograms,
2. step of preparation process and parameter
(1) being dissolved in by acrylamide monomer in 180.0 kilograms of distilled water, and add chain-transferring agent, chelating agent, initiator, 40
Stir 15 minutes under DEG C water bath condition, stand 30 minutes；
(2) under the conditions of 20 DEG C, stir and add 12.0 kilogram sodium hydroxide, be allowed to mix homogeneously, be slow added into
Sodium hypochlorite, stirring reaction 2 hours, add 109.0 kilogram sodium hydroxide, stirring reaction 4 hours；
(3) under the conditions of 15 DEG C, epoxychloropropane is dripped, stirring reaction 0.25h, it is warming up to 80 DEG C, is slowly added dropwise trimethylamine water-soluble
Liquid, reacts 2 hours, is cooled to room temperature.
Embodiment 6
1. raw material group used by the present embodiment following (unit: kilogram)
Acrylamide monomer: 25 kilograms,
Chain-transferring agent (isopropanol and sodium formate mixture, quality proportioning is 1:1): 5.0 kilograms,
Chelating agent (EDTA2Na and acetylacetone,2,4-pentanedione mixture, quality proportioning is 1:1): 2.0 kilograms,
Initiator (sodium sulfite and potassium peroxydisulfate mixture, quality proportioning is 1:1): 2.0 kilograms,
Sodium hydroxide: 150.0 kilograms,
Sodium hypochlorite (10%): 250.0 kilograms,
Epoxychloropropane: 10.0 kilograms,
Trimethylamine: 5.0 kilograms,
Distilled water: 551.0 kilograms,
2. step of preparation process and parameter
(1) being dissolved in by acrylamide monomer in 180.0 kilograms of distilled water, and add chain-transferring agent, chelating agent, initiator, 40
Stir 15 minutes under DEG C water bath condition, stand 20 minutes；
(2) under the conditions of 10 DEG C, stir and add 20.0 kilogram sodium hydroxide, be allowed to mix homogeneously, be slow added into
Sodium hypochlorite, stirring reaction 2 hours, add 130.0 kilogram sodium hydroxide, stirring reaction 4 hours；
(3) under the conditions of 15 DEG C, epoxychloropropane is dripped, stirring reaction 0.25h, it is warming up to 80 DEG C, is slowly added dropwise trimethylamine water-soluble
Liquid, reacts 3 hours, is cooled to room temperature.
Embodiment 7
1. raw material group used by the present embodiment following (unit: kilogram)
Acrylamide monomer: 30.0 kilograms,
Chain-transferring agent (isopropanol, carbamide and sodium formate mixture, quality proportioning is 1:1:1): 10.0 kilograms,
Chelating agent (EDTA2Na and sodium pyrophosphate mixture, quality proportioning is 1:1): 7.5 kilograms,
Initiator (sodium sulfite and potassium peroxydisulfate mixture, quality proportioning is 1:1): 2.0 kilograms,
Sodium hydroxide: 160 kilograms,
Sodium hypochlorite (10%): 224.0 kilograms,
Epoxychloropropane: 9.0 kilograms,
Trimethylamine: 6.0 kilograms,
Distilled water: 551.5 kilograms,
2. step of preparation process and parameter
(1) being dissolved in by acrylamide monomer in 180.0 kilograms of distilled water, and add chain-transferring agent, chelating agent, initiator, 40
Stir 15 minutes under DEG C water bath condition, stand 20 minutes；
(2) under the conditions of 0 DEG C, stir and add 20.0 kilogram sodium hydroxide, be allowed to mix homogeneously, be slow added into secondary
Sodium chlorate, stirring reaction 2 hours, add 140.0 kilogram sodium hydroxide, stirring reaction 4 hours；
(3) under the conditions of 25 DEG C, epoxychloropropane is dripped, stirring reaction 0.2h, it is warming up to 80 DEG C, is slowly added dropwise trimethylamine, reaction
2 hours, it is cooled to room temperature.
Embodiment 8
1. raw material group used by the present embodiment following (unit: kilogram)
Acrylamide monomer: 35.0 kilograms,
Chain-transferring agent (carbamide and isopropanol mixture, quality proportioning is 1:1): 10.0 kilograms,
Chelating agent (EDTA2Na and sodium pyrophosphate mixture, quality proportioning is 1:1): 5.0 kilograms,
Initiator (Ammonium persulfate. and potassium peroxydisulfate mixture, quality proportioning is 1:1): 2.0 kilograms,
Sodium hydroxide: 100.0 kilograms,
Sodium hypochlorite (10%): 250.0 kilograms,
Epoxychloropropane: 9.0 kilograms,
Trimethylamine: 6.0 kilograms,
Distilled water: 583.0 kilograms,
2. step of preparation process and parameter
(1) being dissolved in by acrylamide monomer in 180.0 kilograms of distilled water, and add chain-transferring agent, chelating agent, initiator, 50
Stir 15 minutes under DEG C water bath condition, stand 20 minutes；
(2) under the conditions of 0 DEG C, stir and add 10.0 kilogram sodium hydroxide, be allowed to mix homogeneously, be slow added into secondary
Sodium chlorate, stirring reaction 1.5 hours, add 90.0 kilogram sodium hydroxide, stirring reaction 4 hours；
(3) under the conditions of 25 DEG C, epoxychloropropane is dripped, stirring reaction 0.2h, it is warming up to 70 DEG C, is slowly added dropwise trimethylamine water-soluble
Liquid, reacts 2 hours, is cooled to room temperature.
Performance test:
1, paper making intensifier
(1) as a example by paper making intensifier, the tensile index (Nm/g) of paper is pressed national standard GB/T 22898-by product of the present invention
2008 " mensuration of tensile strength " detect and grade.Its test result is shown in Table 1；
(2) as a example by paper making intensifier, the product of the present invention resistance to broken coefficient (kPam to paper2/ g) by national standard GB/T 454-
2002 " mensuration of paper bursting strength " detect and grade.Its test result is shown in Table 1；
(3) as a example by paper making intensifier, the product of the present invention tear index (Nmm to paper2/ g) by national standard GB/T 455-
2002 " paper and the mensuration of cardboard tearability " detect and grade.Its test result is shown in Table 1；
The different embodiment product of table 1 is to the strength factor of paper after paper effect
2, glue used in paper-making (internal sizing and outer applying glue respectively add 2%)
(1) as a example by glue used in paper-making, the folding strength (secondary) of paper is pressed national standard GB/T 457-2008 " paper by product of the present invention
Mensuration with cardboard folding strength " detect and grade.Its test result is shown in Table 2；
The product of the different embodiment of table 2 is to the folding strength of paper after paper sizing
(2) as a example by glue used in paper-making, the use kiss-coating amount (g/m of product of the present invention2) it is shown in Table 3；
The product of the different embodiment of table 3 is to the kiss-coating amount of product during paper sizing
(3) as a example by glue used in paper-making, the paper break length (km) adding product of the present invention is shown in Table 4；
The product of the different embodiment of table 4 is to the breaking length of paper after paper sizing
(4) as a example by glue used in paper-making, paper machine washable degree (level) adding product of the present invention is shown in Table 5；
The product of the different embodiment of table 5 is to the machine washable degree of paper after paper sizing
(5) as a example by glue used in paper-making, the project Testing index adding product of the present invention is shown in Table 6；
The product of the different embodiment of table 6 is to the project Testing index of paper after paper sizing
3, flocculant
(1) as a example by flocculant, this product is shown in Table 7 to the solid clearance of waste water；
(2) as a example by flocculant, this product is shown in Table 7 to the chroma removal rate of waste water；
(3) as a example by flocculant, this product is shown in Table 7 to the COD clearance of waste water.
The product of the different embodiment of table 7 treatment effect to waste water
The foregoing is only presently preferred embodiments of the present invention, all equalizations done according to scope of the present invention patent change and repair
Decorations, all should belong to the covering scope of the present invention.
Claims (9)
1. the preparation method of a 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer, it is characterised in that: by acryloyl
N put into by amine monomers and distilled water2In the reactor of protection, add chain-transferring agent, chelating agent and initiator, after stirring reaction, then
Successively addition sodium hydroxide, sodium hypochlorite, sodium hydroxide, epoxychloropropane and trimethylamine aqueous solution, prepared 3-ethylene amido-
2-Hydroxyproyl Trimethyl ammonia chloride copolymer.
The preparation method of 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer the most according to claim 1, it is special
Levy and be: acrylamide monomer and distilled water are put into N2In the reactor of protection, add chain-transferring agent, chelating agent and initiation
Agent, 30 ~ 70 DEG C of stirring 10 ~ 30 min, it is cooled to-10 ~ 15 DEG C after standing 10 ~ 30 min, adds sodium hydroxide, stirring is all
It is slowly added to sodium hypochlorite after even, adds sodium hydroxide reaction 2 ~ 4 h after reaction 1 ~ 3 h, drip epoxychloropropane, reaction
It is warming up to 50 ~ 90 DEG C after 0.1 ~ 1.5 h, then is slowly added dropwise trimethylamine aqueous solution after reacting 1 ~ 3 h, be cooled to after reaction 2 ~ 5 h
Room temperature, obtains 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer.
3. according to the method described in claims 1 or 2, it is characterised in that: material component is calculated by weight as:
Acrylamide monomer: 2.0 parts ~ 4.0 parts,
Initiator: 0.05 part ~ 0.2 part,
Chelating agent: 0.1 part ~ 0.5 part,
Chain-transferring agent: 0.1 part ~ 1.0 parts,
Sodium hydroxide: 10.0 parts ~ 20.0 parts,
Sodium hypochlorite: 15.0 parts ~ 25.0 parts,
Epoxychloropropane: 0.2 part ~ 1.0 parts,
Trimethylamine: 0.2 part ~ 1.0 parts,
Distilled water: 40.0 parts ~ 70.0 parts.
4. according to the method described in claims 1 or 2, it is characterised in that: initiator used is Ammonium persulfate., persulfuric acid
The mixture of one or more in potassium, sodium peroxydisulfate, Ammonium persulfate .-sodium sulfite or sodium peroxydisulfate-sodium sulfite.
5. according to the method described in claims 1 or 2, it is characterised in that: chelating agent used be disodiumedetate,
One or more in acetylacetone,2,4-pentanedione, sodium pyrophosphate, aminotriacetic acid, hydroxyethylethylene diamine tri-acetic acid or bicine N-
Mixture.
6. according to the method described in claims 1 or 2, it is characterised in that: chain-transferring agent used is carbamide, isopropanol, first
The mixture of one or more in acid sodium, aliphatic mercaptan or lauryl mercaptan.
7. according to the method described in claims 1 or 2, it is characterised in that: the mass fraction of described sodium hypochlorite is 10%.
8. the 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymerization that a method as claimed in claim 1 or 2 prepares
Thing, it is characterised in that: obtained copolymer is light yellow viscous liquid, solid content >=13%, pH value: 9 ~ 10, the degree of polymerization 80 ~
100, aminating degree is more than 60%.
9. a 3-ethylene amido-2-hydroxypropyl-trimethyl ammonium chloride copolymer as claimed in claim 8 paper strengthening agent,
Application in paper sizing agent or water treatment agent.
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