CN106589298A - Organosilicon-modified cationic aqueous polyurethane paper wet strength agent and preparation method - Google Patents

Organosilicon-modified cationic aqueous polyurethane paper wet strength agent and preparation method Download PDF

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Publication number
CN106589298A
CN106589298A CN201610979498.XA CN201610979498A CN106589298A CN 106589298 A CN106589298 A CN 106589298A CN 201610979498 A CN201610979498 A CN 201610979498A CN 106589298 A CN106589298 A CN 106589298A
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aqueous polyurethane
silicon
organic
organosilicon
wet strength
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张晓蕾
仇晓龙
李彦涛
陈孝起
周海军
周萌萌
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Energy Research Institute of Hebei Academy of Sciences
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Energy Research Institute of Hebei Academy of Sciences
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    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
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    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6685—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3225 or polyamines of C08G18/38
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    • C08G18/6688—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • 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
    • D21H19/10—Coatings without pigments
    • D21H19/12—Coatings without pigments applied as a solution using water as the only solvent, e.g. in the presence of acid or alkaline compounds
    • 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

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Abstract

The invention relates to the technical field of chemistry, and in particular to an organosilicon-modified cationic aqueous polyurethane paper wet strength agent and a preparation method. The organosilicon-modified cationic aqueous polyurethane paper wet strength agent consists of the following materials: polyether diol, tertiary amino polyether diol, polyether triol, dibutyltin dilaurate, isocyanate, cationic hydrophilic chain extender, end-capping agent, glacial acetic acid, acetone, organosilicon modifier and water. The invention introduces tertiary amino groups into both a soft segment structure and a hard segment structure, quaternary ammonium cations are generated after acid neutralization, consequently, the cationic degree is increased, and the organosilicon-modified cationic aqueous polyurethane paper wet strength agent can be better adsorbed on paper fibers with negative charges, and can be quickly and completely retained; by organosilicon modification, crosslinking density is increased, a chemical network structure is formed, and the organosilicon-modified cationic aqueous polyurethane paper wet strength agent which has a high cationic degree and high wet strength can be formed when used on paper; with water as dispersant, the organosilicon-modified cationic aqueous polyurethane paper wet strength agent is nontoxic, pollution-free and highly compatible, and the existence of free formaldehyde and organic halide in conventional wet strength agents are prevented, so the organosilicon-modified cationic aqueous polyurethane paper wet strength agent is environment-friendly and safe.

Description

A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking and preparation method
Technical field
The present invention relates to technical field of chemistry, and in particular to a kind of organic-silicon-modified cation aqueous polyurethane paper is wet strong Agent and preparation method.
Background technology
Aqueous polyurethane (WPU) is with water as solvent, good, easily modified with nontoxic, pollution-free, the safe and reliable, compatibility The features such as, there is preferably application in fields such as coating, adhesive, textile and papers.Dissociate in traditional paper wet strength agent The precipitation of formaldehyde and the presence of organochlorine can cause certain injury to environment and human body, thus aqueous polyurethane in recent years into For the focus of paper industry wet strength agent research.Terminated-type cation water-borne polyurethane can produce electrostatic with the hydroxyl in paper fiber and inhale Draw, form physical crosslinking, to a certain degree increase paper strength, while the closing of active isocyanate base is stored, and heat When reaching deblocking temperature, originally the isocyanate groups of closing are released, and with cellulose macromolecule chain on reactivity There is chemical crosslinking in group, improve the wet strength of paper.But it is the hardness of single terminated-type cation water-borne polyurethane film, resistance to Aqueouss, mechanical property are poor, have impact on its promotion and application in terms of wet strengthening agents for papermaking to a certain extent.Cationic and Reactivity is to improve two essential conditions of wet strengthening agents for papermaking, is mainly reflected in improve cation in cation aqueous polyurethane Degree and crosslinking, enhancing and modifying.
China Patent Publication No. CN102796237B disclose double hydroxyl cationic hydrophilic chain extenders and its synthesis sun from Application in sub- aqueous pu dispersions, the invention have synthesized a kind of cationic hydrophilic of the glycol of the tertiary amine groups containing secondary alcohol Chain extender, is prepared for cation aqueous polyurethane dispersion, can be used for the middle bottom covering with paint of corium, artificial leather, the back cover of timber Paint, the sizing agent of paper surface, anti pilling agent, fabric color fixing agent and antistatic additive in weaving process.The invention is with most of sun Ion water-based polyurethane seemingly, makees chain extender using tertiary amine groups glycol, so as to obtain the cationic water of hard section cation group Property polyurethane.The method directly affects rigid polyurethane for the consumption that raising cationic degree has limitation, tertiary amino chain extender The physical crosslinking of intersegmental hydrogen bond, excessive use can cause serious phase separation, so as to destroy the mechanical property of material.
Organic siliconresin has the advantages that low-surface-energy, water-fast, high-low temperature resistant and fire-retardant, in existing preparation method, mainly Based on the linear polysiloxane modified aqueous polyurethane containing active group, resistance to water is improved, but serious phase point From causing, emulsion storage stability and painting film dynamic performance be not good enough.
The content of the invention
It is an object of the invention to overcome the deficiencies in the prior art, there is provided a kind of cationic degree is high, crosslinking mechanical property is good Organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking and preparation method.
The purpose of the present invention is achieved through the following technical solutions：
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, including following raw material is in parts by weight：
Further, the molecular weight of the PTMEG is 1000-2000, and the molecular weight of the tertiary amino PTMEG is 500-2000, the molecular weight of the polyether triol is 500-2000；Specifically, the PTMEG be polyoxypropyleneglycol, At least one of Polyoxyethylene glycol, polytetrahydrofuran diol；The tertiary amino PTMEG is tertiary amino polyethylene glycol oxide Glycol；The polyether triol is polypropylene oxide triol.
Further, the PTMEG is polyoxypropyleneglycol that molecular weight is 1000 or PolyTHF two Alcohol；The tertiary amino PTMEG is tertiary amino Polyoxyethylene glycol that molecular weight is 1000；The polyether triol is molecule Measure the polypropylene oxide triol for 1000.
Further, 5-20% of the tertiary amino PTMEG consumption for PTMEG total moles content, the polyethers The mol ratio of glycol and polyether triol is 1.5-9：1.
Further, the isocyanates are toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, isophorone two At least one in isocyanates, isocyanate index are 1.1～1.3.
Further, dihydroxy compounds of the cationic hydrophilic chain extender for tertiary-amino-containing.
Further, the end-capping reagent be methyl ethyl ketoxime, imidazoles, any one in sodium sulfite, its consumption is isocyanide The 1-20% of acid esters molar content.
Further, the organosilicon modifier is N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, its 1-20% of the consumption for isocyanates molar content.
Further, the end-capping reagent and the mol ratio of organosilicon modifier are 0.5-2：1.
The preparation method of above-mentioned organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, comprises the following steps：
S1. by PTMEG, tertiary amino PTMEG, polyether triol, dibutyl tin laurate and isocyanates in 65- 2-3h is reacted at 80 DEG C；
S2. 40 DEG C are cooled to, cationic hydrophilic chain extender is added, 2-3h is reacted；
S3. end-capping reagent reaction 2-3h is added, glacial acetic acid is added and is formed quaternary ammonium salt cationic, obtain base polyurethane prepolymer for use as；
S4. hydration organosilicon modifier is added, emulsion dispersion 1-2h obtains organic-silicon-modified cation aqueous polyurethane Wet strengthening agents for papermaking；
In above-mentioned preparation process, by adding acetone regulation system viscosity.
Further, the consumption of the cationic hydrophilic chain extender for base polyurethane prepolymer for use as gross mass 5～10%.
Further, methods described before carrying out also include pre-treatment step, the pretreatment be specially by PTMEG, Tertiary amino PTMEG and polyether triol carry out 1.5h evacuation processed at 110-120 DEG C.
The application of above-mentioned organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is applied to paper surface and processes or wet Strengthen in portion.
The principle of the present invention：Introduce tertiary amino in polyurethane molecular Soft hard segment structure in pairs, and changed by organosilicon Property, solve aqueous polyurethane cationic degree it is low, the bad problem of mechanical property；Tertiary amino PTMEG is introduced into polyurethane soft section In, reacted with isocyanates after being dried with PTMEG, polyether triol mixed dehydration, add cation chain extender, sealed Close, neutralize, disperse, be modified, obtain organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking；The present invention improves aqueouss and gathers The cationic degree of urethane, strong with the adhesion of paper fiber, solution is honored as a queen and can be reacted with the hydroxyl on paper fiber surface, organosilicon It is modified for paper surface process and wet end strengthen in, be remarkably improved paper mechanical property.
The invention has the beneficial effects as follows：The present invention breaches the preparation method of traditional cation aqueous polyurethane, in molecule Introduce tertiary amino in soft section and hard segment structure in pairs, quaternary ammonium salt cationic is formed Jing after acid neutralization, improve cationic degree, preferably Absorption can be kept in negatively charged paper fiber quick and completely；By organic-silicon-modified, crosslink density is improved, formed Chemical network structure, is used on paper forming a kind of cationic degree height, the good organic-silicon-modified cationic water of wet strength Property polyurethane wet strengthening agents for papermaking；, with water as dispersant, nontoxic, pollution-free, the safe and reliable, compatibility is good, avoid biography for the present invention In system wet strength agent, the presence of free formaldehyde and organohalogen compounds, is conducive to environmental protection.
Specific embodiment
Technical scheme is described in further detail with reference to specific embodiment, but protection scope of the present invention is not It is confined to described below.
Embodiment 1
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared by the following method and forms：
S1. by the number-average molecular weight through evacuation processed be 1000 tertiary amino polyoxyethylene glycol 11.1g, Polytetrahydrofuran diol 100g and polypropylene oxide triol 49.3g are added in the four-hole bottle equipped with reflux condenser, stirring, plus Heat heats up, and when temperature rises to 65-80 DEG C, adds 0.001g dibutyl tin laurates, isoflurane chalcone diisocyanate 102.8g With acetone 37ml, 2-3h is reacted；
S2. 40 DEG C are cooled to, N, N- dimethyl diethanolamine 22.1g is added, suitable rate of addition is controlled, acetone is added 18ml reduces viscosity, chain extending reaction 2-3h；
S3. methyl ethyl ketoxime 3.2g reaction 2-3h are subsequently added, glacial acetic acid 11.8g are added and is formed quaternary ammonium salt cationic, knot Shu Fanying obtains base polyurethane prepolymer for use as；
S4. it is eventually adding deionized water 700.7g and N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane The mixed liquor high speed emulsion dispersion 1-2h of 15.3g, obtains the organic-silicon-modified cation aqueous polyurethane paper that solid content is 30% Open wet strength agent.
Embodiment 2
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared from by 1 methods described of embodiment, bag Include following raw material：Tertiary amino polyoxyethylene glycol 5g, polytetrahydrofuran diol 100g, polypropylene oxide triol 46.7g, different fluorine that Ketone diisocyanate 93.4g, N, N- dimethyl diethanolamine 20.9g, methyl ethyl ketoxime 3.1g, glacial acetic acid 10.8g, deionized water 662.9g, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 15.3g.
Embodiment 3
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared from by 1 methods described of embodiment, bag Include following raw material：Tertiary amino polyoxyethylene glycol 25g, polytetrahydrofuran diol 100g, polypropylene oxide triol 55.4g, different fluorine You are ketone diisocyanate 115g, N, N- dimethyl diethanolamine 25g, methyl ethyl ketoxime 3.5g, glacial acetic acid 15g, deionized water 800g, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 18g.
Embodiment 4
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared from by 1 methods described of embodiment, bag Include following raw material：Tertiary amino polyoxyethylene glycol 11.1g, polytetrahydrofuran diol 100g, polypropylene oxide triol 12.3g are different Fluorine that ketone diisocyanate 71.9g, N, N- dimethyl diethanolamine 15.5g, methyl ethyl ketoxime 3.3g, glacial acetic acid 8.5g, deionization Water 517.1g, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 10.7g.
Embodiment 5
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared from by 1 methods described of embodiment, bag Include following raw material：Tertiary amino polyoxyethylene glycol 11.1g, polytetrahydrofuran diol 100g, polypropylene oxide triol 4g, different fluorine that Ketone diisocyanate 65g, N, N- dimethyl diethanolamine 14.7g, methyl ethyl ketoxime 3.1g, glacial acetic acid 8.1g, deionized water 450g, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 10.2g.
Embodiment 6
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared from by 1 methods described of embodiment, bag Include following raw material：Tertiary amino polyoxyethylene glycol 11.1g, polyoxypropyleneglycol 100g, polypropylene oxide triol 49.3g are different Fluorine your ketone diisocyanate 102.8g, N, N- dimethyl diethanolamine 22.1g, methyl ethyl ketoxime 3.2g, glacial acetic acid 11.8g, go from Sub- water 700.7g, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 15.3g.
Embodiment 7
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared from by 1 methods described of embodiment, bag Include following raw material：Tertiary amino polyoxyethylene glycol 11.1g, polytetrahydrofuran diol 100g, polypropylene oxide triol 49.3g are different Fluorine your ketone diisocyanate 102.8g, N, N- dimethyl diethanolamine 22.1g, methyl ethyl ketoxime 8.1g, glacial acetic acid 11.8g, go from Sub- water 712.1g, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 9.5g.
Embodiment 8
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared from by 1 methods described of embodiment, bag Include following raw material：Tertiary amino polyoxyethylene glycol 25g, polytetrahydrofuran diol 100g, number-average molecular weight are 2000 polyoxygenated Propylene triol 112g, isoflurane chalcone diisocyanate 115g, N, N- dimethyl diethanolamine 25g, methyl ethyl ketoxime 15g, glacial acetic acid 14.1g, deionized water 880g, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 8.8g.
Embodiment 9
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared from by 1 methods described of embodiment, bag Include following raw material：Tertiary amino polyoxyethylene glycol 5.6g, polytetrahydrofuran diol 100g, number-average molecular weight are 500 polyoxygenated Propylene triol 4g, isoflurane chalcone diisocyanate 65g, N, N- dimethyl diethanolamine 14g, imidazoles 3g, glacial acetic acid 7.4g, go from Sub- water 450g, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 3.5g.
Embodiment 10
A kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, is prepared from by 1 methods described of embodiment, bag Include following raw material：Tertiary amino polyoxyethylene glycol 11.1g, polytetrahydrofuran diol 100g, polypropylene oxide triol 49.3g are different Fluorine your ketone diisocyanate 102.8g, N, N- dimethyl diethanolamine 22.1g, methyl ethyl ketoxime 12.9g, glacial acetic acid 11.8g, go from Sub- water 723.3g, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane 3.8g.
The above is only the preferred embodiment of the present invention, it should be understood that the present invention is not limited to described herein Form, is not to be taken as the exclusion to other embodiment, and can be used for various other combinations, modification and environment, and can be at this In the text contemplated scope, it is modified by the technology or knowledge of above-mentioned teaching or association area.And those skilled in the art are entered Capable change and change, then all should be in the protection domains of claims of the present invention without departing from the spirit and scope of the present invention It is interior.

Claims (10)

1. a kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking, it is characterised in that including following raw material with weight Part meter：
2. a kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking according to claim 1, it is characterised in that The molecular weight of the PTMEG is 1000-2000, and the molecular weight of the tertiary amino PTMEG is 500-2000, the polyethers The molecular weight of triol is 500-2000；Specifically, the PTMEG is polyoxypropyleneglycol, Polyoxyethylene glycol, gathers At least one of erythritan；The tertiary amino PTMEG is tertiary amino Polyoxyethylene glycol；The polyether triol For polypropylene oxide triol.
3. a kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking according to claim 1, it is characterised in that The tertiary amino PTMEG consumption is rubbing for the 5-20% of PTMEG total moles content, the PTMEG and polyether triol You are than being 1.5-9：1.
4. a kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking according to claim 1, it is characterised in that The isocyanates are toluene di-isocyanate(TDI), methyl diphenylene diisocyanate, in isoflurane chalcone diisocyanate at least One kind, isocyanate index are 1.1～1.3.
5. a kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking according to claim 1, it is characterised in that Dihydroxy compounds of the cationic hydrophilic chain extender for tertiary-amino-containing.
6. a kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking according to claim 1, it is characterised in that The end-capping reagent is methyl ethyl ketoxime, imidazoles, any one in sodium sulfite, 1- of its consumption for isocyanates molar content 20%.
7. a kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking according to claim 1, it is characterised in that The organosilicon modifier is N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane, and its consumption is isocyanates mole The 1-20% of content.
8. a kind of organic-silicon-modified cation aqueous polyurethane wet strengthening agents for papermaking according to claim 1, it is characterised in that The end-capping reagent is 0.5-2 with the mol ratio of organosilicon modifier：1.
9. a kind of preparation of cation aqueous polyurethane wet strengthening agents for papermaking organic-silicon-modified as described in claim 1-8 any one Method, it is characterised in that comprise the following steps：
S1. by PTMEG, tertiary amino PTMEG, polyether triol, dibutyl tin laurate and isocyanates at 65-80 DEG C Lower reaction 2-3h；
S2. 40 DEG C are cooled to, cationic hydrophilic chain extender is added, 2-3h is reacted；
S3. end-capping reagent reaction 2-3h is added, glacial acetic acid is added and is formed quaternary ammonium salt cationic, obtain base polyurethane prepolymer for use as；
S4. water and organosilicon modifier are added, emulsion dispersion 1-2h obtains organic-silicon-modified cation aqueous polyurethane paper Wet strength agent；
In above-mentioned preparation process, by adding acetone regulation system viscosity.
10. a kind of cation aqueous polyurethane wet strengthening agents for papermaking organic-silicon-modified as described in claim 1-8 any one should With, it is characterised in that it is applied to paper surface and processes or wet end reinforcement.
CN201610979498.XA 2016-11-08 2016-11-08 Organosilicon-modified cationic aqueous polyurethane paper wet strength agent and preparation method Pending CN106589298A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107129676A (en) * 2017-06-15 2017-09-05 天津大学 Cation aqueous polyurethane-chitosan blend thing and preparation method thereof
CN108424502A (en) * 2018-02-27 2018-08-21 合肥微晶材料科技有限公司 A kind of multifunctional monomer and the low square resistance flexible transparent conducting film based on it
CN110317314A (en) * 2019-07-23 2019-10-11 潍坊科技学院 A kind of paper grade (stock) aqueous polyurethane and preparation method thereof
CN111019082A (en) * 2019-12-16 2020-04-17 东南大学 Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101805438A (en) * 2010-04-13 2010-08-18 江苏工业学院 Preparation method and applications of cationic waterborne polyurethane surface sizing agent
US20110182844A1 (en) * 2007-08-14 2011-07-28 Momentive Performance Materials Gmbh Novel Polyurea- and/or Polyurethane-Polyorganosiloxane Compounds
CN102277122A (en) * 2011-03-30 2011-12-14 烟台联成高分子材料有限公司 Waterborne polyurethane adhesive and manufacturing method thereof
CN102731746A (en) * 2012-06-29 2012-10-17 上海东升新材料有限公司 Enclosed type aqueous polyurethane emulsion papermaking wet strength agent and its preparation method
CN102796237A (en) * 2012-08-31 2012-11-28 合肥安科精细化工有限公司 Dihydroxyl cationic hydrophilic chain extender and application thereof to synthesis of cationic aqueous polyurethane dispersoid

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110182844A1 (en) * 2007-08-14 2011-07-28 Momentive Performance Materials Gmbh Novel Polyurea- and/or Polyurethane-Polyorganosiloxane Compounds
CN101805438A (en) * 2010-04-13 2010-08-18 江苏工业学院 Preparation method and applications of cationic waterborne polyurethane surface sizing agent
CN102277122A (en) * 2011-03-30 2011-12-14 烟台联成高分子材料有限公司 Waterborne polyurethane adhesive and manufacturing method thereof
CN102731746A (en) * 2012-06-29 2012-10-17 上海东升新材料有限公司 Enclosed type aqueous polyurethane emulsion papermaking wet strength agent and its preparation method
CN102796237A (en) * 2012-08-31 2012-11-28 合肥安科精细化工有限公司 Dihydroxyl cationic hydrophilic chain extender and application thereof to synthesis of cationic aqueous polyurethane dispersoid

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
宋远波等: "自交联型阳离子水性聚氨酯纸张增强剂的制备及其应用", 《中华纸业》 *
李新平等: "异氰酸酯类纸张增强剂的应用", 《造纸化学品与应用》 *
翁丽青等: "封闭异氰酸酯的合成及在造纸中的应用", 《造纸化学品》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107129676A (en) * 2017-06-15 2017-09-05 天津大学 Cation aqueous polyurethane-chitosan blend thing and preparation method thereof
CN108424502A (en) * 2018-02-27 2018-08-21 合肥微晶材料科技有限公司 A kind of multifunctional monomer and the low square resistance flexible transparent conducting film based on it
CN108424502B (en) * 2018-02-27 2020-06-16 合肥微晶材料科技有限公司 Multifunctional monomer and low-sheet-resistance flexible transparent conductive film based on same
CN110317314A (en) * 2019-07-23 2019-10-11 潍坊科技学院 A kind of paper grade (stock) aqueous polyurethane and preparation method thereof
CN111019082A (en) * 2019-12-16 2020-04-17 东南大学 Nonionic photo-curing polyurethane aqueous dispersion resin composition with excellent compatibility and preparation method and application thereof

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Application publication date: 20170426