CN105061653B - A kind of 1 urea groups 2 hydroxypropyl vinylamine copolymer and its preparation method and application - Google Patents
A kind of 1 urea groups 2 hydroxypropyl vinylamine copolymer and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of 1 urea groups 2 hydroxypropyl vinylamine copolymer and its preparation method and application, acrylamide monomer and distilled water are put into N2In the reactor of protection, add chain-transferring agent, chelating agent and initiator, 30 ~ 70 DEG C of stirring 10 ~ 30min; it is cooled to 10 ~ 15 DEG C after standing 10 ~ 30min, add sodium hydroxide, after stirring, be slowly added to sodium hypochlorite; sodium hydroxide is added after reaction 1 ~ 3h; it is warming up to 50 ~ 90 DEG C after 2 ~ 4h, be slowly added dropwise the mixed solution of epoxychloropropane and carbamide, after reaction 2 ~ 5h, be cooled to room temperature; obtain final product 1 urea groups 2 hydroxypropyl vinylamine copolymer; for light yellow viscous liquid, solid content >=13%, pH value：9 ~ 10, the degree of polymerization 80 ~ 100, aminating degree, can be used as paper strengthening agent, paper sizing agent or flocculant more than 60%.Preparation process is simple, raw materials for production are easy to get, with short production cycle, and reaction is gentle, is convenient for industrialized great production, has a extensive future.
Description
Technical field
The invention belongs to fine chemistry industry, environment-friendly material and additive for paper making, water treatment agent field are and in particular to one kind
1- urea groups -2- hydroxypropyl vinylamine copolymer and its preparation method and application.
Background technology
With the raising of level of consumption, people's also more and more higher of the requirement to paper class and quality, how to improve paper
Intensity meeting the direction that the demand of people is that people study always.Traditional method to improve long stapled proportioning by making beating
With the intensity strengthening paper using reinforcing agent, wherein, pull an oar and existed by long stapled proportioning both approaches more
Defect, as big in power consumption, drainability is low, tearability dies down, and paper additive is not because having the problems referred to above and quilt
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
The dry, wet strength opened, rub resistance degree and folding strength etc..Paper strength be subject between the intensity of pulp fiber itself and fiber or
Bond strength between coating, the impact of area etc. is larger, 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 exactly to be contained by it
The copolymer of specific groups makes to form hydrogen bond between cellulosic molecule thus improving intensity and the properties of paper[3].
Starch based additive is also one of research emphasis of people, but general starch based paper making intensifier is to fiber molecule
The raising of horizontal integration area is limited, and conventional size agent emulsion is used cationic starch as emulsifying agent and stabilizer, but such is newborn
Retention on fiber for the liquid is low, slower with fiber-reactive, and the applying glue time is long[4,5], and, starch based reinforcing agent is with sizing agent also
More grain resource will be consumed, the present invention mainly studies polyvinylamine as the technique of additive for paper making and its application[6].
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 moreover it is possible to carry out network with metal ion with aldehydes, anhydrides, carboxylic acidss, halogenated hydrocarbons etc.
Close, prepare other functions type macromolecular material.Its molecular chain length and charge density also can be adjusted according to practical application request
Section, therefore have very wide application prospect.
Tanaka[7,8,9]Aminating degree being obtained under cryogenic with polyacrylamide and substantial amounts of sodium hydroxide is 96%
Polyvinylamine, research finds, amide groups have once carried out N- chloroamides, be just no longer converted into carboxylic acid group, suitably
Controlling the concentration of sodium hypochlorite, the hydrolysis of amide being suppressed in very low level, thus preparing the product of certain aminating degree
Thing；Achari et al.[10]Numerous studies are carried out to Hofmann reaction synthesizing polyethylene amine, he thinks in presence 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[11]Hofmann reaction with cross-linked polyacrylamide as raw material be studies have shown that, the degree of polymerization low for improve raw material
Polyacrylamide degradation rate is favourable, and sums up the optimal conditionss of synthesizing cross-linked polyvinylamine.
Wherein, hoffman degradation reaction formula is as follows：
Chen Fushan et al.[12]Have studied the potentiation to paper industry for the polyvinylamine, test result indicate that, PVAm is in different pH
Charge density under value is different, and the charge density of acid condition is higher than alkalescence condition.As reinforcing agent, the aminating degree of PVAm is got over
Height, reinforced effects are better.When system pH value is 4～9, add the PVAm that 0.2% consumption, aminating degree are 30% ~ 50% to bleaching
Hardwood pulp and bleaching needle-point leaf pulp mixing slurry have significant potentiation.King's root et al.[13]Inquire into polyvinylamine to change
Property agent impact that cultural paper is produced, result shows, polyvinylamine modifying agent can not only improve the retention of filler, improves
The tensile strength of paper, can also reduce the consumption of polyacrylamide (PAM) and the proportioning of softwood pulp simultaneously, produce to reducing
Cost has good effect.Peng Tianxing et al.[14]Using polyvinylamine, waste paper deinking waste water is processed, well and cationic
Polyacrylamide is compared, test result indicate that：Polyvinylamine has good decolouring and goes turbid performance. processing negative charge amount
Higher waste water aspect is advantageous.
Instant invention overcomes conventional size agent makes fiber in slurry, filler etc. occur, wadding is poly-, precipitation the problems such as, not anti-
Answer generation stickum in kettle, while ensureing that sizing efficiency is excellent, ill effect is not produced to paper-making process auxiliary agent；And not
Containing formaldehyde, low toxic and environment-friendly, belong to environment-friendly material.
List of references：
[1] Beijing Forestry University. cationic sheet paper reinforcing agent and its production 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, applies Herba Cymbidii Goeringii, remaining loyalty forever etc. the application [J] that polyvinylamine produces in Cultural Paper. Chinese paper industry,
2013,(21): 25-28.
[4] Shanghai dongsheng New Materials Co., Ltd. surface sizing agent emulsion and its preparation method and application:China,
CN201310287674.X[P].2013-11-27.
[5] Tianjin University of Commerce. a kind of preparation method of composite surface sizing agent:China, CN201310728623.6
[P].2014-4-2.
[6] king builds, Zhou Xiaowei, Lian Anfeng etc. and polyvinylamine substitutes the research that cationic starch makees paper making intensifier
[J]. Chinese paper industry, 2010,31 (16):36-38.
[7] Tanak H, Senju R. Preparation of polyvinylamine by Hofmann
degradation of polyacrylamide [J].Bull. Chem. Soc. Jpn.,1976,49(10):2821-
2823.
[8] 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.
[9] 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.
[10] 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.
[11] Zhang Zhenqian, Lu Jianmei, Wang Lihua etc. the synthesis of cross-linked polyvinylamine and performance study [J]. oil
Work, 2002,31 (4): 254-258.
[12] Chen Fushan, Guo Zhen, Wang Lijun etc. the preparation of polyvinylamine and its research [J] as paper making intensifier.
Chinese papermaking, 2007,26 (4): 27-30.
[13] king's root, Wang Wei, Hu Haitao etc. application [J] in cultural paper production for the polyvinylamine filling modifier.
Chinese papermaking, 2013,32 (9): 11-14.
[14] 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.
Content of the invention
It is an object of the invention to provide a kind of 1- urea groups -2- hydroxypropyl vinylamine copolymer and preparation method thereof and should
With can strengthen tensile index, resistance to broken coefficient and the tear index of paper as paper strengthening agent；Can as paper sizing agent
Increase paper break length, folding strength and machine washable degree；The colourity of waste water can be removed as flocculant, reduce CODCrValue.Preparation work
Skill is easy, 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：
A kind of preparation method of 1- urea groups -2- hydroxypropyl vinylamine copolymer：Acrylamide monomer and distilled water are put into
N2In the reactor of protection, add chain-transferring agent, chelating agent and initiator, 30 ~ 70 DEG C of stirring 10 ~ 30min, stand 10 ~ 30min
After be cooled to -10 ~ 15 DEG C, add sodium hydroxide, after stirring, be slowly added to sodium hypochlorite, after reaction 1 ~ 3h, add hydrogen-oxygen
Change sodium, after 2 ~ 4h, be warming up to 50 ~ 90 DEG C, be slowly added dropwise the mixed solution of epoxychloropropane and carbamide, be cooled to after reaction 2 ~ 5h
Room temperature, obtains final product 1- urea groups -2- hydroxypropyl vinylamine copolymer.
Raw material components are counted by weight：
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
Carbamide：0.2 part ~ 0.6 part
Distilled water：40.0 parts ~ 70.0 parts.
Described initiator be Ammonium persulfate., potassium peroxydisulfate, sodium peroxydisulfate, Ammonium persulfate ./sodium sulfite, sodium peroxydisulfate/
One or more of sodium sulfite.
Described chelating agent is disodiumedetate, acetylacetone,2,4-pentanedione, sodium pyrophosphate, aminotriacetic acid, N- ethoxy
Ethylenediamine triacetic acid, N, one or more of N- bicine N-.
Described chain-transferring agent be one of carbamide, isopropanol, sodium formate, aliphatic mercaptan, lauryl mercaptan or
Several.
Prepared 1- urea groups -2- hydroxypropyl vinylamine 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%.
Prepared 1- urea groups -2- hydroxypropyl vinylamine copolymer is as paper strengthening agent, paper sizing agent or flocculant.
Compared with prior art, the present invention has following remarkable advantage：
1. in the present invention, epoxychloropropane open loop in the basic conditions, and in the presence of carbamide, decrease polymer side
The content of chlorinated organics in chain, decrease the probability crosslinking between molecule, it is to avoid the generation of gel, improves product
The stability of product, and reduce the residual content of the chlorinated organics such as epoxychloropropane.So the 1- urea groups of present invention preparation-
2- hydroxypropyl vinylamine copolymer has formaldehydeless, and chlorinated organics are few, low toxicity, the advantage of environmental protection.
2. the 1- urea groups -2- hydroxypropyl vinylamine copolymer prepared in the present invention, can strengthen paper as paper strengthening agent
Tensile index, resistance to broken coefficient and the tear index opened；Paper break length, folding strength and resistance to machine can be increased as paper sizing agent
Degree of washing.Meanwhile, this product preparation process is simple, and raw materials for production are easy to get, with short production cycle, and reaction is gentle, and equipment needed thereby is routine
Equipment, is convenient for industrialized great production.
3. in the present invention preparation 1- urea groups -2- hydroxypropyl vinylamine copolymer, use it for paper surface coating, can be with
Hydroxyl reaction on fiber, produces effective cover layer on surface, improves its color fastness and fastness to rubbing, can increase wrinkle simultaneously
Recovery angle, folding strength and tearability, improve the print gloss of paper, have good feel.
4. the 1- urea groups -2- hydroxypropyl vinylamine copolymer prepared in the present invention, can effectively go eliminating water as flocculant
In float and colloidal substance, reduce water in CODCrValue, strong adaptability, good decolorizing effect, papermaking can be widely used in and give up
The industries such as water, light textile, printing and dyeing.
The reaction equation of the present invention is as follows：
Specific embodiment
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 chain-transferring agents, 0.1 part ~ 0.5 part chelating agent and 0.05 part ~ 0.2 part initiator, 30 ~ 70 DEG C of stirrings 10 ~
30min, is cooled to -10 ~ 15 DEG C after standing 10 ~ 30min, adds 2.0 parts of sodium hydroxide, be slowly added to 10.0 parts after stirring
~ 20.0 parts of sodium hypochlorite, add 8.0 parts ~ 18.0 parts sodium hydroxide after reaction 1 ~ 3h, are warming up to 50 ~ 90 DEG C, slowly after 2 ~ 4h
0.2 part ~ 1.0 parts epoxychloropropane of Deca and the mixed solution of 0.2 part ~ 0.6 part of carbamide, are cooled to room temperature, that is, after reaction 2 ~ 5h
Obtain 1- urea groups -2- hydroxypropyl vinylamine copolymer.
Raw material quality fraction is：
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
Carbamide：0.2 part ~ 0.6 part
Distilled water：40.0 parts ~ 70.0 parts
Following examples added medicine summation is 1000 kilograms.
Wherein, sodium hydroxide distilled water adds after being configured to 30% ~ 40% solution.
Embodiment 1：
1. the raw material group used by the present embodiment is as follows（Unit：Kilogram）
Acrylamide monomer：22.0 kilograms
Chain-transferring agent（Carbamide）：4.0 kilogram
Chelating agent（EDTA2Na）：2.0 kilogram
Initiator（Ammonium persulfate. and sodium peroxydisulfate mixture, quality proportioning is 1:1）：2.0 kilogram
Sodium hydroxide：121.0 kilogram
Sodium hypochlorite（10%）：224.0 kilogram
Epoxychloropropane：6.0 kilogram
Carbamide：4.0 kilogram
Distilled water：614.0 kilogram
2. step of preparation process and parameter
（1）22.0 kilograms of monomers are dissolved in 215.0 kilograms of distilled water, and add 4.0 kilograms of chain-transferring agents, 2.0 kilograms
Chelating agent, 2.0 kilograms of initiators, stir 15 minutes under 40 DEG C of 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, more slowly
Add 224.0 kilograms of sodium hypochlorite, stirring reaction 2 hours, add 109.0 kilogram sodium hydroxide, 2 hours of stirring reaction.
（3）Stir under the conditions of 60 DEG C, be slowly added dropwise 6.0 kilograms of epoxychloropropane, react 2 hours.Continue to add urine
4.0 kilograms of element, reacts 2 hours, is cooled to room temperature.
Embodiment 2：
1. the raw material group used by the present embodiment is as follows（Unit：Kilogram）
Acrylamide monomer：22.0 kilograms
Chain-transferring agent（Carbamide）：5.0 kilogram
Chelating agent（EDTA2Na）：2.0 kilogram
Initiator（Ammonium persulfate.）：1.0 kilogram
Sodium hydroxide：121.0 kilogram
Sodium hypochlorite（10%）：224.0 kilogram
Epoxychloropropane：6.0 kilogram
Carbamide:6.0 kilogram
Distilled water：615.0 kilogram
2. step of preparation process and parameter
（1）22.0 kilograms of monomers are dissolved in 180.0 kilograms of distilled water, and add 5.0 kilograms of chain-transferring agents, 2.0 kilograms
Chelating agent, 1.6 kilograms of initiators, stir 20 minutes under 40 DEG C of water bath condition, stand 20 minutes.
（2）Under the conditions of 0 DEG C, stir and add 12.0 kilogram sodium hydroxide, be allowed to mix homogeneously, more slowly add
Enter 224.0 kilograms of sodium hypochlorite, stirring reaction 2 hours, add 109.0 kilogram sodium hydroxide, 4 hours of stirring reaction.
（3）Stir under the conditions of 70 DEG C, be slowly added dropwise 9.0 kilograms of epoxychloropropane, react 2 hours.Continue to add urine
6.0 kilograms of element, reacts 2 hours.
Embodiment 3：
1. the raw material group used by the present embodiment is as follows（Unit：Kilogram）
Acrylamide monomer：22.0 kilograms
Chain-transferring agent（Carbamide and isopropanol mixture, quality proportioning is 1:1）：5.0 kilogram
Chelating agent（EDTA2Na）：2.0 kilogram
Initiator（Sodium peroxydisulfate and potassium peroxydisulfate mixture, quality proportioning is 1:1）：1.0 kilogram
Sodium hydroxide：121.0 kilogram
Sodium hypochlorite（10%）：224.0 kilogram
Epoxychloropropane：6.0 kilogram
Carbamide：4.0 kilogram
Distilled water：615.0 kilogram
2. step of preparation process and parameter
（1）22.0 kilograms of monomers are dissolved in 215.0 kilograms of distilled water, and add 5.0 kilograms of chain-transferring agents, 2.0 kilograms
Chelating agent, 1.0 kilograms of initiators, stir 15 minutes under 50 DEG C of 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, more slowly
Add 224.0 kilograms of sodium hypochlorite, stirring reaction 2 hours, add 109.0 kilogram sodium hydroxide, 4 hours of stirring reaction.
（3）Stir under the conditions of 70 DEG C, be slowly added dropwise 6.0 kilograms of epoxychloropropane, react 2 hours.Continue to add urine
4.0 kilograms of element, reacts 2 hours.
Embodiment 4：
1. the raw material group used by the present embodiment is as follows（Unit：Kilogram）
Acrylamide monomer：20.0 kilograms
Chain-transferring agent（Carbamide and isopropanol mixture, quality proportioning is 1:1）：8.0 kilogram
Chelating agent（EDTA2Na and HEDTA mixture, quality proportioning is 1:1）：2.0 kilogram
Initiator（Sodium peroxydisulfate and sodium peroxydisulfate/sodium sulfite mixture, quality proportioning is 1:1）：1.0 kilogram
Sodium hydroxide：100. 0 kilograms
Sodium hypochlorite（10%）：250.0 kilogram
Epoxychloropropane：6.0 kilogram
Carbamide：2.0 kilogram
Distilled water：611.0 kilogram
2. step of preparation process and parameter
（1）20.0 kilograms of monomers are dissolved in 180.0 kilograms of distilled water, and add 8.0 kilograms of chain-transferring agents, 2.0 kilograms
Chelating agent, 1.0 kilograms of initiators, stir 15 minutes under 50 DEG C of water bath condition, stand 20 minutes.
（2）Under the conditions of 5 DEG C, stir and add 10 kilogram sodium hydroxide, be allowed to mix homogeneously, be slow added into
250.0 kilograms of sodium hypochlorite, stirring reaction 2 hours, add double centner sodium hydroxide, 4 hours of stirring reaction.
（3）Stir under the conditions of 70 DEG C, be slowly added dropwise 6.0 kilograms of epoxychloropropane, react 2 hours.Continue to add urine
2.0 kilograms of element, reacts 1 hour.
Embodiment 5：
1. the raw material group used by the present embodiment is as follows（Unit：Kilogram）
Acrylamide monomer：26.0 kilograms
Chain-transferring agent（Carbamide and isopropanol mixture, quality proportioning is 1:1）：10.0 kilograms
Chelating agent（EDTA2Na and DEG mixture, quality proportioning is 1:1）：2.0 kilogram
Initiator（Sodium peroxydisulfate and potassium peroxydisulfate mixture, quality proportioning is 1:1）：2.0 kilogram
Sodium hydroxide：130.0 kilogram
Sodium hypochlorite（10%）：200.0 kilogram
Epoxychloropropane：6.0 kilogram
Carbamide：6.0 kilogram
Distilled water：618.0 kilogram
2. step of preparation process and parameter
（1）26.0 kilograms of monomers are dissolved in 200 kilograms of distilled water, and add 10.0 kilograms of chain-transferring agents, 2.0 kilograms of networks
Mixture, 12.0 kilograms of initiators, stir 20 minutes under 50 DEG C of water bath condition, stand 30 minutes.
（2）Under the conditions of 10 DEG C, stir and add 15.0 kilogram sodium hydroxide, be allowed to mix homogeneously, more slowly
Add 200.0 kilograms of sodium hypochlorite, stirring reaction 2 hours, add 115.0 kilogram sodium hydroxide, 4 hours of stirring reaction.
（3）Stir under the conditions of 80 DEG C, be slowly added dropwise 6.0 kilograms of epoxychloropropane, react 1 hour.Continue to add urine
6.0 kilograms of element, reacts 2 hours.
Embodiment 6：
1. the raw material group used by the present embodiment is as follows（Unit：Kilogram）
Acrylamide monomer：30.0 kilograms
Chain-transferring agent（Isopropanol and sodium formate mixture, quality proportioning is 1:1）：10.0 kilograms
Chelating agent（EDTA2Na and acetylacetone,2,4-pentanedione mixture, quality proportioning is 1:1）：2.0 kilogram
Initiator（Sodium sulfite and potassium peroxydisulfate mixture, quality proportioning is 1:1）：1.0 kilogram
Sodium hydroxide：121.0 kilogram
Sodium hypochlorite（10%）：200.0 kilogram
Epoxychloropropane：6.0 kilogram
Carbamide：6.0 kilogram
Distilled water：624.0 kilogram
2. step of preparation process and parameter
（1）30.0 kilograms of monomers are dissolved in 200 kilograms of distilled water, and add 10 kilograms of chain-transferring agents, 2.0 kilograms of complexations
Agent, 1.0 kilograms of initiators, stir 15 minutes under 50 DEG C of water bath condition, stand 30 minutes.
（2）Under the conditions of 10 DEG C, stir and add 13 kilogram sodium hydroxide, be allowed to mix homogeneously, more slowly add
Enter 200.0 kilograms of sodium hypochlorite, stirring reaction 2 hours, add 108 kilogram sodium hydroxide, 4 hours of stirring reaction.
（3）Stir under the conditions of 70 DEG C, be slowly added dropwise 6.0 kilograms of epoxychloropropane, react 2 hours.Continue to add urine
6.0 kilograms of element, reacts 3 hours.
Embodiment 7：
1. the raw material group used by the present embodiment is as follows（Unit：Kilogram）
Acrylamide monomer：22.0 kilograms
Chain-transferring agent（Carbamide）：5.0 kilogram
Chelating agent（EDTA2Na and aminotriacetic acid mixture, quality proportioning is 1:1）：3.0 kilogram
Initiator（Sodium sulfite and potassium peroxydisulfate mixture, quality proportioning is 1:1）：2.0 kilogram
Sodium hydroxide：121.0.0 kilogram
Sodium hypochlorite（10%）：230.0 kilogram
Epoxychloropropane：6.0 kilogram
Carbamide：4.0 kilogram
Distilled water：607.0 kilogram
2. step of preparation process and parameter
（1）22.0 kilograms of monomers are dissolved in 200 kilograms of distilled water, and add 5.0 kilograms of chain-transferring agents, 3.0 kilograms of networks
Mixture, 2.0 kilograms of initiators, stir 20 minutes under 40 DEG C of water bath condition, stand 20 minutes.
（2）Under the conditions of 0 DEG C, stir and add 12.0 kilogram sodium hydroxide, be allowed to mix homogeneously, more slowly add
Enter 230.0 kilograms of sodium hypochlorite, stirring reaction 2 hours, add 109.0 kilogram sodium hydroxide, 5 hours of stirring reaction.
（3）Stir under the conditions of 70 DEG C, be slowly added dropwise 6.0 kilograms of epoxychloropropane, react 2 hours.Continue to add urine
4.0 kilograms of element, reacts 2 hours.
Embodiment 8：
1. the raw material group used by the present embodiment is as follows（Unit：Kilogram）
Acrylamide monomer：25.0 kilograms
Chain-transferring agent（Carbamide and isopropanol mixture, quality proportioning is 1:1）：7.0 kilogram
Chelating agent（Acetylacetone,2,4-pentanedione and aminotriacetic acid mixture, quality proportioning is 1:1）：2.0 kilogram
Initiator（Sodium sulfite and Ammonium persulfate ./sodium sulfite mixture, quality proportioning is 1:1）：2.0 kilogram
Sodium hydroxide：180.0 kilogram
Sodium hypochlorite（10%）：170.0 kilogram
Epoxychloropropane：6.0 kilogram
Carbamide：4.0 kilogram
Distilled water：604.0 kilogram
2. step of preparation process and parameter
（1）25.0 kilograms of monomers are dissolved in 200 kilograms of distilled water, and add 7.0 kilograms of chain-transferring agents, 2.0 kilograms of networks
Mixture, 2.0 kilograms of initiators, stir 20 minutes under 40 DEG C of 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, more slowly
Add 170.0 kilograms of sodium hypochlorite, stirring reaction 2 hours, add 160.0 kilogram sodium hydroxide, 6 hours of stirring reaction.
（3）Stir under the conditions of 70 DEG C, be slowly added dropwise 6.0 kilograms of epoxychloropropane, react 2 hours.Continue to add urine
4.0 kilograms of element, reacts 2 hours.
Performance test：
1：Paper making intensifier
（1）Taking paper making intensifier as a example, the tensile index to paper for the product of the present invention（Nm/g）By national standard GB/T
22898-2008《The mensure of tensile strength》To detect and to grade.Its test result is shown in Table 1；
（2）Taking paper making intensifier as a example, the resistance to broken coefficient to paper for the product of the present invention（kPam2/g）By national standard GB/T
454-2002《The mensure of paper bursting strength》To detect and to grade.Its test result is shown in Table 1；
（3）Taking paper making intensifier as a example, the tear index to paper for the product of the present invention（Nmm2/g）：National standard GB/T
455-2002《Paper and the mensure of cardboard tearability》To detect and to grade.Its test result is shown in Table 1；
The strength factor to paper after paper effect for the different embodiment product of table 1
2：Glue used in paper-making（Internal sizing is each with outer applying glue to add 2%）
（1）Taking glue used in paper-making as a example, the folding strength to paper for the product of the present invention（Secondary）By national standard GB/T 457-2008
《Paper and the mensure of cardboard folding strength》To detect and to grade.Its test result is shown in Table 2；
The folding strength to paper after paper sizing for the product of the different embodiment of table 2
（2）Taking glue used in paper-making as a example, the use kiss-coating amount (g/m of product of the present invention2) it is shown in Table 3；
The kiss-coating amount to product during paper sizing for the product of the different embodiment of table 3
（3）, the paper break length (km) adding product of the present invention is shown in Table 4 taking glue used in paper-making as a example；
The breaking length to paper after paper sizing for the product of the different embodiment of table 4
（4）, paper machine washable degree (level) adding product of the present invention is shown in Table 5 taking glue used in paper-making as a example；
The machine washable degree to paper after paper sizing for the product of the different embodiment of table 5
3：Flocculant
（1）As a example flocculant, this product is shown in Table 6 to the solid clearance of waste water；
（2）, this product is shown in Table 6 to the chroma removal rate of waste water taking flocculant as a example；
（3）, this product is shown in Table 6 to the COD clearance of waste water taking flocculant as a example.
The treatment effect to waste water for the product of the different embodiment of table 6
The foregoing is only presently preferred embodiments of the present invention, all impartial changes done according to scope of the present invention patent with
Modify, all should belong to the covering scope of the present invention.
Claims (7)
1. a kind of preparation method of 1- urea groups -2- hydroxypropyl vinylamine copolymer it is characterised in that：By acrylamide monomer and steaming
Distilled water puts into N2In the reactor of protection, add chain-transferring agent, chelating agent and initiator, 30 ~ 70 DEG C of stirring 10 ~ 30min, standing
It is cooled to -10 ~ 15 DEG C after 10 ~ 30min, adds sodium hydroxide, be slowly added to sodium hypochlorite after stirring, after reaction 1 ~ 3h again
Add sodium hydroxide, after 2 ~ 4h, be warming up to 50 ~ 90 DEG C, be slowly added dropwise the mixed solution of epoxychloropropane and carbamide, react 2 ~ 5h
After be cooled to room temperature, obtain final product 1- urea groups -2- hydroxypropyl vinylamine copolymer.
2. method according to claim 1 it is characterised in that：Raw material components are counted by weight：
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
Carbamide：0.2 part ~ 0.6 part
Distilled water：40.0 parts ~ 70.0 parts.
3. method according to claim 1 and 2 it is characterised in that：Described initiator be Ammonium persulfate., potassium peroxydisulfate,
One or more of sodium peroxydisulfate, Ammonium persulfate ./sodium sulfite, sodium peroxydisulfate/sodium sulfite.
4. method according to claim 1 and 2 it is characterised in that：Described chelating agent is disodiumedetate, second
Acyl acetone, sodium pyrophosphate, aminotriacetic acid, N-hydroxyethyl-ethylenediamine triacetic acid, N, one of N- bicine N- or
Several.
5. method according to claim 1 and 2 it is characterised in that：Described chain-transferring agent is carbamide, isopropanol, formic acid
One or more of sodium, aliphatic mercaptan.
6. a kind of the method for claim 1 be obtained 1- urea groups -2- hydroxypropyl vinylamine copolymer it is characterised in that：
Prepared 1- urea groups -2- hydroxypropyl vinylamine copolymer is light yellow viscous liquid, solid content >=13%, pH value：9 ~ 10, polymerization
Degree 80 ~ 100, aminating degree is more than 60%.
7. the application of the 1- urea groups -2- hydroxypropyl vinylamine copolymer that a kind of the method for claim 1 is obtained, its feature
It is：Prepared 1- urea groups -2- hydroxypropyl vinylamine copolymer is as paper strengthening agent, paper sizing agent or flocculant.
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| CN101481890A (en) * | 2008-04-28 | 2009-07-15 | 湖北嘉韵化工科技有限公司 | Efficient surface sizing agent |
| CN103924480A (en) * | 2014-04-04 | 2014-07-16 | 诸城市奥尼生物科技有限公司 | Formula and preparation method of functionalized enhancer for papermaking |
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| CN101225621A (en) * | 2008-02-20 | 2008-07-23 | 福建师范大学 | Multifunctional macromolecule paper making promoter and preparation method thereof |
| CN101481890A (en) * | 2008-04-28 | 2009-07-15 | 湖北嘉韵化工科技有限公司 | Efficient surface sizing agent |
| CN103924480A (en) * | 2014-04-04 | 2014-07-16 | 诸城市奥尼生物科技有限公司 | Formula and preparation method of functionalized enhancer for papermaking |
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