CN101302731B - Method for preparing organosilicon modified paper sheet humidifying strong agent - Google Patents
Method for preparing organosilicon modified paper sheet humidifying strong agent Download PDFInfo
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- CN101302731B CN101302731B CN2008100183971A CN200810018397A CN101302731B CN 101302731 B CN101302731 B CN 101302731B CN 2008100183971 A CN2008100183971 A CN 2008100183971A CN 200810018397 A CN200810018397 A CN 200810018397A CN 101302731 B CN101302731 B CN 101302731B
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Abstract
The invention discloses a preparation method of a paper wet strengthening agent that is modified by organic silicon, which comprises the following steps: firstly combines the raw materials of dibasic acid and polyhydric amine into a polyamine intermediate compound of daiamid. A certain amount of the polyamine intermediate compound of daiamid, epoxy chloropropane and an organosilane coupling agentare taken to react under certain temperature so as to achieve certain viscosity, and the reaction is halted by adding acid, thus obtaining the paper wet strengthening agent that is modified by organic silicon. The preparation method of the paper wet strengthening agent that is modified by organic silicon can reduce the usage of the epoxy chloropropane and lower the organic chlorine content in discharged substances; the cross-linked product greatly increases molecular weight and active crosslinking points of molecular chain sections. The product of the paper wet strengthening agent that is modified by organic silicon achieves greatly raised retention degree, can improve not only the wet strength of paper but also the paper physical performance such as folding resistance, tensile strength and dry strength, etc., and the superficial water-proof performance of paper can be greatly raised if the paper wet strengthening agent is coated on the surface of paper.
Description
Technical field
The invention belongs to fine chemicals preparation technology field, particularly a kind of preparation method of organosilicon modified paper sheet humidifying strong agent.
Background technology
Numerous paper products especially industrial paper all require to have higher wet strength.Polyamide epoxy polyamine chloropropane (PAE) as the maximum wet reinforcing agent of present application, has traditional wet strength agent Lauxite (UF), modified melamine-formaldehyde resin (MF) and the incomparable advantage of acrylamide copolymer.It not only has good wet potent fruit and slurry performance again, and does not have free formaldehyde in process of production, to ecological environment and health close friend.Existing PAE preparation method makes with epichlorohydrin reaction then normally by adipic acid and diethylenetriamine or triethylene tetramine prepared in reaction polyamine under alkali condition.This series products is because the Non-crosslinked modification, and its crosslinking degree, molecular weight are lower, and retention performance is poor, and the wet potent fruit of paper does not far reach production requirement, and is particularly still undesirable to the effect of ask for something high wet strength paper kind; Bring many harmful effects can for simultaneously manufacturing paper with pulp of paper, easily produce bubble, wad a quilt with cotton and gather as slurry, the page uniformity is poor, and rigidity is low etc.
Summary of the invention
The objective of the invention is to overcome the shortcoming of above-mentioned prior art, provide a kind of and can in paper pulp, have the high retention performance, the preparation method of wet potent fruit and environment amenable organosilicon modified paper sheet humidifying strong agent.
For achieving the above object, the technical solution used in the present invention is: with polyamine and binary acid by 0.7-1.5: 1 mol ratio joins in the dry reactor, be heated to 140-200 ℃, made the polyamide polyamines in the reactor reach 100-160mPas in insulation reaction 3-7 hour at 25 ℃ viscosity, add deionized water, it is 50% that the polyamide polyamines is diluted to solid content, obtains the solution A of wet strength agent intermediate; With solution A, epoxychloropropane and organo silane coupling agent by 100: after the mass ratio of 1-40: 1-5 mixes, it is 20% that the adding deionized water is diluted to solid content with system, in 50-80 ℃ of reaction 1-6 hour, when 25 ℃ of following system viscositys reach 20-60mPas, stop heating, being diluted to solid content with deionized water is 10%-15%, sour regulation system pH to 1-4, get final product organosilicon modified paper sheet humidifying strong agent.
Polyamine of the present invention adopts a kind of or wherein mixing of more than one arbitrary proportions in diethylenetriamine, triethylene tetramine, the tetraethylene pentamine; Binary acid is a succinic acid, a kind of or wherein mixing of more than one arbitrary proportions in adipic acid, fumaric acid, the maleic acid etc.; Acid is a kind of in hydrochloric acid, glacial acetic acid, formic acid, sulfuric acid, the nitric acid or the mixture of more than one arbitrary proportions wherein; Organo silane coupling agent is a MTMS, MTES, methyl triacetoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, γ-mercaptopropyl trimethoxysilane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-r-chloropropyl trimethoxyl silane, γ-chloropropyl triethoxysilane, three amido propyl group methyl dimethoxysilanes, cyanoethyl methyl dimethoxysilane, methyl tributanoximo silane, the vinyl tributanoximo silane, a kind of in γ-glycidyl ether oxygen propyl trimethoxy silane or the mixture of more than one arbitrary proportions wherein.
Preparation process of the present invention is not added organic solvent, and no free formaldehyde discharges, and can reduce simultaneously and send the organic content of organic chloride of thing, to ecological environment and health close friend; And introduce organo silane coupling agent as crosslinking agent, make molecular weight product obtain certain raising, and improved the retention performance of modified polyamide epoxy polyamine chloropropane greatly, under low consumption, can make paper reach desirable wet potent fruit; Simultaneously, the introducing of crosslinking agent has increased the crosslinking active of molecule segment, further strengthened the affinity of polymer and fiber, and around the fiber intensity of formed staggered chain structure, thereby limit fiber and interfibrous activity better, stop the swollen and the suction of fiber, reduce performances such as page dilatation, increase substantially the wet strength of paper.In addition, this invention product can not only improve the wet strength of paper, and can increase the physical properties such as folding strength, tensile strength and dry strength of paper, as uses it for the paper surface coating, also can increase substantially the surperficial WATER RESISTANCE of paper.
The specific embodiment
Embodiment 1: polyamine diethylenetriamine and the binary acid succinic acid mol ratio by 1.0: 1 is joined in the dry reactor, be heated to 200 ℃, insulation reaction made the viscosity of the polyamide polyamines in the reactor reach 100mPa.s in 5 hours, and (the product viscosity is at 25 ℃, polyamide polyamines solid content is to measure under 50% condition), add deionized water, it is 50% that the polyamide polyamines is diluted to solid content, obtains the solution A of wet strength agent intermediate; After solution A, epoxychloropropane and organo silane coupling agent MTMS mixed by 100: 20: 2 mass ratio, it is 20% that the adding deionized water is diluted to solid content with system, in 80 ℃ of reactions 1 hour, when the system viscosity reaches 20mPa.s (the product viscosity is measured down at 25 ℃), stop heating, being diluted to solid content with deionized water is 15%, with hydrochloric acid regulation system pH to 1, get final product organic-silicon-modified polyamide epoxy polyamine chloropropane paper wet strength agent.
Embodiment 2: polyamine triethylene tetramine and the binary acid adipic acid mol ratio by 0.8: 1 is joined in the dry reactor, be heated to 180 ℃, insulation reaction made the viscosity of the polyamide polyamines in the reactor reach 150mPa.s in 7 hours, and (the product viscosity is at 25 ℃, polyamide polyamines solid content is to measure under 50% condition), add deionized water, it is 50% that the polyamide polyamines is diluted to solid content, obtains the solution A of wet strength agent intermediate; After solution A, epoxychloropropane and organo silane coupling agent MTES mixed by 100: 5: 4 mass ratio, it is 20% that the adding deionized water is diluted to solid content with system, in 70 ℃ of reactions 3 hours, when the system viscosity reaches 30mPa.s (the product viscosity is measured down at 25 ℃), stop heating, being diluted to solid content with deionized water is 12%, with glacial acetic acid regulation system pH to 3, get final product organic-silicon-modified polyamide epoxy polyamine chloropropane paper wet strength agent.
Embodiment 3: polyamine tetraethylene pentamine and the binary acid fumaric acid mol ratio by 1.2: 1 is joined in the dry reactor, be heated to 150 ℃, insulation reaction made the viscosity of the polyamide polyamines in the reactor reach 130mPa.s in 3 hours, and (the product viscosity is at 25 ℃, polyamide polyamines solid content is to measure under 50% condition), add deionized water, it is 50% that the polyamide polyamines is diluted to solid content, obtains the solution A of wet strength agent intermediate; After solution A, epoxychloropropane and organo silane coupling agent methyl triacetoxysilane mixed by 100: 30: 1 mass ratio, it is 20% that the adding deionized water is diluted to solid content with system, in 60 ℃ of reactions 5 hours, when the system viscosity reaches 40mPa.s (the product viscosity is measured down at 25 ℃), stop heating, being diluted to solid content with deionized water is 10%, with formic acid regulation system pH to 2, get final product organic-silicon-modified polyamide epoxy polyamine chloropropane paper wet strength agent.
Embodiment 4: polyamine diethylenetriamine and triethylene tetramine are joined in the dry reactor with the mixture of arbitrary proportion and the binary acid maleic acid mol ratio by 0.7: 1, be heated to 170 ℃, insulation reaction made the viscosity of the polyamide polyamines in the reactor reach 160mPa.s in 6 hours, and (the product viscosity is at 25 ℃, polyamide polyamines solid content is to measure under 50% condition), add deionized water, it is 50% that the polyamide polyamines is diluted to solid content, obtains the solution A of wet strength agent intermediate; After solution A, epoxychloropropane and organo silane coupling agent phenyltrimethoxysila,e mixed by 100: 1: 3 mass ratio, it is 20% that the adding deionized water is diluted to solid content with system, in 50 ℃ of reactions 6 hours, when the system viscosity reaches 50mPa.s (the product viscosity is measured down at 25 ℃), stop heating, being diluted to solid content with deionized water is 13%, with sulfuric acid regulation system pH to 4, get final product organic-silicon-modified polyamide epoxy polyamine chloropropane paper wet strength agent.
Embodiment 5: polyamine diethylenetriamine, triethylene tetramine and tetraethylene pentamine are joined in the dry reactor with the mixture of the arbitrary proportion mol ratio by 1.4: 1 with the mixture of arbitrary proportion and binary acid succinic acid and adipic acid, be heated to 140 ℃, insulation reaction made the viscosity of the polyamide polyamines in the reactor reach 120mPa.s in 4 hours, and (the product viscosity is at 25 ℃, polyamide polyamines solid content is to measure under 50% condition), add deionized water, it is 50% that the polyamide polyamines is diluted to solid content, obtains the solution A of wet strength agent intermediate; After solution A, epoxychloropropane and organo silane coupling agent phenyl triethoxysilane mixed by 100: 25: 5 mass ratio, it is 20% that the adding deionized water is diluted to solid content with system, in 55 ℃ of reactions 4 hours, when the system viscosity reaches 60mPa.s (the product viscosity is measured down at 25 ℃), stop heating, being diluted to solid content with deionized water is 11%, with nitric acid regulation system pH to 1, get final product organic-silicon-modified polyamide epoxy polyamine chloropropane paper wet strength agent.
Embodiment 6: polyamine diethylenetriamine and tetraethylene pentamine are joined in the dry reactor with the mixture of the arbitrary proportion mol ratio by 0.9: 1 with the mixture of arbitrary proportion and binary acid fumaric acid and maleic acid, be heated to 160 ℃, insulation reaction made the viscosity of the polyamide polyamines in the reactor reach 140mPa.s in 3 hours, and (the product viscosity is at 25 ℃, polyamide polyamines solid content is to measure under 50% condition), add deionized water, it is 50% that the polyamide polyamines is diluted to solid content, obtains the solution A of wet strength agent intermediate; After solution A, epoxychloropropane and organo silane coupling agent dimethoxydiphenylsilane mixed by 100: 10: 1 mass ratio, it is 20% that the adding deionized water is diluted to solid content with system, in 65 ℃ of reactions 2 hours, when the system viscosity reaches 35mPa.s (the product viscosity is measured down at 25 ℃), stop heating, being diluted to solid content with deionized water is 14%, with hydrochloric acid and glacial acetic acid mixture regulation system pH to 4 with arbitrary proportion, get final product organic-silicon-modified polyamide epoxy polyamine chloropropane paper wet strength agent.
Embodiment 7: polyamine tetraethylene pentamine and the binary acid adipic acid mol ratio by 1.5: 1 is joined in the dry reactor, be heated to 190 ℃, insulation reaction made the viscosity of the polyamide polyamines in the reactor reach 110mPa.s in 7 hours, and (the product viscosity is at 25 ℃, polyamide polyamines solid content is to measure under 50% condition), add deionized water, it is 50% that the polyamide polyamines is diluted to solid content, obtains the solution A of wet strength agent intermediate; With solution A, after epoxychloropropane and organo silane coupling agent γ-chloropropyl triethoxysilane and γ-chloropropyl triethoxysilane mix by 100: 40: 5 mass ratio with the mixture of arbitrary proportion, it is 20% that the adding deionized water is diluted to solid content with system, in 75 ℃ of reactions 5 hours, when the system viscosity reaches 55mPa.s (the product viscosity is measured down at 25 ℃), stop heating, being diluted to solid content with deionized water is 10%, with formic acid and sulfuric acid mixture regulation system pH to 3 with arbitrary proportion, get final product organic-silicon-modified polyamide epoxy polyamine chloropropane paper wet strength agent.
The present invention can reduce the epoxychloropropane consumption, has reduced content of organic chloride in the effluent; Its molecular weight of product after organo-silicon coupling agent is crosslinked increases greatly, and the crosslinking active point of molecule segment increases.This wet strength agent retention is greatly improved, it can not only improve the wet strength of paper, and can increase the physical properties such as folding strength, tensile strength and dry strength of paper, and as use it for the paper surface coating, also can increase substantially the surperficial WATER RESISTANCE, surface strength of paper etc.
Claims (5)
1. the preparation method of organosilicon modified paper sheet humidifying strong agent is characterized in that:
1) with polyamine and binary acid by 0.7-1.5: 1 mol ratio joins in the dry reactor, be heated to 140-200 ℃, made the polyamide polyamines in the reactor reach 100-160mPas in insulation reaction 3-7 hour at 25 ℃ viscosity, add deionized water, it is 50% that the polyamide polyamines is diluted to solid content, obtains the solution A of wet strength agent intermediate;
2) with solution A, epoxychloropropane and organo silane coupling agent by 100: after the mass ratio of 1-40: 1-5 mixes, it is 20% that the adding deionized water is diluted to solid content with system, in 50-80 ℃ of reaction 1-6 hour, when 25 ℃ of following system viscositys reach 20-60mPas, stop heating, being diluted to solid content with deionized water is 10%-15%, sour regulation system pH to 1-4, get final product organosilicon modified paper sheet humidifying strong agent.
2. the preparation method of organosilicon modified paper sheet humidifying strong agent according to claim 1 is characterized in that: described polyamine is a kind of in diethylenetriamine, triethylene tetramine, the tetraethylene pentamine or the mixture of more than one arbitrary proportions wherein.
3. the preparation method of organosilicon modified paper sheet humidifying strong agent according to claim 1, it is characterized in that: described binary acid is a succinic acid, a kind of in adipic acid, fumaric acid, the maleic acid or the mixture of more than one arbitrary proportions wherein.
4. the preparation method of organosilicon modified paper sheet humidifying strong agent according to claim 1 is characterized in that: described acid is a kind of in hydrochloric acid, glacial acetic acid, formic acid, sulfuric acid, the nitric acid or the mixture of more than one arbitrary proportions wherein.
5. the preparation method of organosilicon modified paper sheet humidifying strong agent according to claim 1, it is characterized in that: described organo silane coupling agent is a MTMS, MTES, methyl triacetoxysilane, phenyltrimethoxysila,e, phenyl triethoxysilane, dimethoxydiphenylsilane, γ-mercaptopropyl trimethoxysilane, N-β-aminoethyl-γ-An Bingjisanjiayangjiguiwan, γ-r-chloropropyl trimethoxyl silane, γ-chloropropyl triethoxysilane, three amido propyl group methyl dimethoxysilanes, the cyanoethyl methyl dimethoxysilane, methyl tributanoximo silane, vinyl tributanoximo silane, a kind of in γ-glycidyl ether oxygen propyl trimethoxy silane or the mixture of more than one arbitrary proportions wherein.
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| CN2008100183971A CN101302731B (en) | 2008-06-06 | 2008-06-06 | Method for preparing organosilicon modified paper sheet humidifying strong agent |
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| CN2008100183971A CN101302731B (en) | 2008-06-06 | 2008-06-06 | Method for preparing organosilicon modified paper sheet humidifying strong agent |
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101831072B (en) * | 2010-03-31 | 2012-06-20 | 上海东升新材料有限公司 | Water-proofing agent for coated paper coatings and preparation method thereof |
| CN101831070B (en) * | 2010-03-31 | 2011-11-16 | 上海东升新材料有限公司 | Modified coating water repellent agent and preparation method thereof |
| CN101929109B (en) * | 2010-09-21 | 2012-03-07 | 浙江池禾化工有限公司 | Active diluent modified paper wet strength agent and preparation method thereof |
| CN102535249B (en) * | 2011-12-31 | 2014-04-02 | 杭州杭化哈利玛化工有限公司 | Novel wet strengthening agent for papermaking and preparation method and application thereof |
| CN102898643B (en) * | 2012-10-12 | 2014-03-12 | 陕西科技大学 | Preparation method of modified polyarylether (PAE) resin |
| CN103030806B (en) * | 2012-12-14 | 2014-10-08 | 华南理工大学 | High-solid content polyamide polyamine epichlorohydrin wet strength agent, as well as preparation and application thereof |
| CN103396544A (en) * | 2013-07-01 | 2013-11-20 | 陕西科技大学 | Method for preparing a reinforcing agent special for ultrafine glass fiber paper and applications of reinforcing agent |
| CN103951812B (en) * | 2014-04-22 | 2016-08-24 | 浙江传化华洋化工有限公司 | A kind of preparation method of epoxy polyamide class wet strength agent for papermaking |
| CN106087563A (en) * | 2016-06-20 | 2016-11-09 | 广州聚注专利研发有限公司 | The preparation method of a kind of wet strength agent and wet strength agent |
| CN109610227A (en) * | 2018-11-22 | 2019-04-12 | 山东同创精细化工股份有限公司 | A kind of low chlorine ion wet strength agent and preparation method thereof |
| CN109629335A (en) * | 2019-01-02 | 2019-04-16 | 江苏富淼科技股份有限公司 | A kind of paper for daily use wet strength agent and preparation method thereof |
| CN114213654B (en) * | 2021-12-31 | 2023-10-20 | 浙江百斯特化工有限公司 | Preparation method of cationic polyamide wet strength agent, product and application thereof |
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Application publication date: 20081112 Assignee: Suzhou Heng Kang new material Co., Ltd Assignor: Shaanxi University of Science and Technology Contract record no.: 2013320010127 Denomination of invention: Method for preparing organosilicon modified paper sheet humidifying strong agent Granted publication date: 20100728 License type: Exclusive License Record date: 20130702 |
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