WO2020000310A1 - Crosslinking modified type water-soluble solid polyacrylamide and use thereof - Google Patents

Crosslinking modified type water-soluble solid polyacrylamide and use thereof Download PDF

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Publication number
WO2020000310A1
WO2020000310A1 PCT/CN2018/093383 CN2018093383W WO2020000310A1 WO 2020000310 A1 WO2020000310 A1 WO 2020000310A1 CN 2018093383 W CN2018093383 W CN 2018093383W WO 2020000310 A1 WO2020000310 A1 WO 2020000310A1
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Prior art keywords
monomer
soluble solid
polyacrylamide
modified
solid polyacrylamide
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PCT/CN2018/093383
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French (fr)
Chinese (zh)
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史亚鹏
魏星光
王勤
何国锋
郭志宇
李国红
闫武军
于胜利
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江苏富淼科技股份有限公司
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Priority to PCT/CN2018/093383 priority Critical patent/WO2020000310A1/en
Publication of WO2020000310A1 publication Critical patent/WO2020000310A1/en

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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
    • C08F220/00—Copolymers 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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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

Definitions

  • the invention belongs to the field of water-soluble polymer materials, and particularly relates to a cross-linked modified water-soluble solid polyacrylamide and use thereof.
  • Polyacrylamide as an excellent industrial additive can be divided into three types: aqueous solution type, emulsion type, and solid type (or called powder type) according to the product status. According to its chargeability, it can be divided into cationic polyacrylamide, anionic polyacrylamide, nonionic polyacrylamide, and amphoteric polyacrylamide.
  • Amphoteric polyacrylamide has an anionic and cationic group in its molecule, which makes its application range more and more. Compared with polyacrylamide containing a single anionic group or cationic group, it not only has the comprehensive properties of the two at the same time, but also has obvious anti-polyelectrolyte effect and a wide range of pH adaptation. These properties and characteristics are The extensive application of amphoteric polyacrylamide provides strong support.
  • the aqueous solution amphoteric polyacrylamide products on the market are used to strengthen the sheet in papermaking, and the effect is obvious. Especially, it is widely used to enhance the secondary reuse fiber reinforcement.
  • the water-based amphoteric polyacrylamide products also have the following problems: First, the molecular weight is low, mostly between 300,000 and 600,000. If higher molecular weight products are needed, the viscosity of the aqueous solution will increase as the molecular weight increases, affecting the product. Flowability, which further affects the use (liquid transportation and dissolution become difficult); the solid content of aqueous products is low, which is basically around 15% -20% on the market, exceeding 25% is very rare.
  • amphoteric polyacrylamide liquid products contain a large amount of water, the product is prone to mildew during storage. At the same time, the ester group in its molecular structure is easily hydrolyzed, resulting in changes in the molecular structure of the polymer and affecting the use effect.
  • amphoteric polyacrylamide liquid products due to the low solid content, lead to high transportation costs and high packaging costs. 4. Shelf life of amphoteric polyacrylamide liquid products is short. The actual shelf life of most products is only three months, and the longest is no more than six months.
  • Hu Huiren disclosed the preparation of polyacrylamide with acrylamide, methacryloyloxyethyltrimethylammonium chloride, acrylic acid, and N-methylol acrylamide as main raw materials. Under the condition of aqueous solution polymerization reaction, the reaction temperature rises sharply at 20% (see: Temperature control in the production process of AmPAM paper dry strength agent [J] China Papermaking, 2014, 33 (12): 19-23).
  • Chinese patent CN107366182A discloses an acrylamide polymer, which is a polymer of a polymerization component including a (meth) acrylamide, a quaternary ammonium monomer, and a (meth) allyl sulfonate, and Does not contain nitrogen-containing crosslinkable monomers and tertiary amino-based monomers.
  • the prepared polyacrylamide is an aqueous solution type with low effective content, high transportation cost, and easy hydrolysis.
  • the purpose of the present invention is to provide a cross-linked modified water-soluble solid polyacrylamide product, which can solve the problems of low molecular weight, low effective content, poor storage stability, short shelf life, and the like of the aqueous type amphoteric polyacrylamide product. Obtain higher molecular weight products, high effective content, low transportation cost, not easy to hydrolyze, not easy to mold.
  • the invention also provides the use of the water-soluble solid polyacryl in the reinforcement and / or modification of natural fiber materials or semi-synthetic fiber materials.
  • the present invention adopts the following technical scheme:
  • the said water-soluble solid polyacrylamide is composed of at least a nonionic monomer A, a nonionic monomer B, a crosslinking agent, a modified monomer, and a cationic monomer.
  • anionic monomers are obtained by chain polymerization of six types of monomers.
  • the structure of the six types of monomers is as follows:
  • the structure of the non-ionic monomer A is as follows:
  • R 1 represents H or CH 3 ;
  • R 2 and R 3 represent H, CH 3 , CH 2 CH 3 or
  • the non-ionic monomer B is selected from a combination of one or more of the compounds represented by the following general formula II-1, II-2, and II-3:
  • R 4 represents H or CH 3 ;
  • R 5 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
  • R 6 and R 7 represent H, CH 3 , CH 2 CH 3 or
  • R 8 represents H or CH 3 ;
  • R 9 and R 11 and R 12 represent H, CH 3 , CH 2 CH 3 or
  • R 10 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
  • R 13 represents H or CH 3 ;
  • R 14 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
  • R 15 and R 16 represent H, CH 3 , CH 2 CH 3 or
  • the cross-linking agent has a general structural formula of the following formula III-1, III-2, III-3, III-4, III-5, III-6, or III-7:
  • R 17 represents OH or CH 3 ;
  • R 18 , R 19 and R 20 represent
  • R 21 , R 22 and R 23 represent CH 2 or CH 2 CH 2 ;
  • R 24 , R 25 , R 26 , and R 27 represent CH 2 and CH 2 CH 2 .
  • the modified monomer includes one or two of modified monomer A and modified monomer B;
  • the modified monomer A includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, acrylonitrile, hydroxymethacrylamide, styrene, vinylpyrrolidone, 4 -One or more of vinylpyridine and (meth) acrylate monomers;
  • the structural formula IV of the (meth) acrylate monomer is as follows:
  • R 28 represents H or CH 3 ;
  • R 29 represents H, CH 3 , (CH 2 ) n CH 3 , and n ⁇ 6 (n is an integer).
  • the modified monomer B is an organic silicon monomer, and specifically includes 3- (N-allylamino) propyltrimethoxysilane, dimethyl (dimethylamino) vinylsilane, allyl ( One or two of diisopropylamino) dimethylsilane, vinyl-tris (2-methoxyethoxy) silane, allyltrimethoxysilane, or a compound represented by the general formula (V) Species and a mixture of two or more species in an amount of 0.5 wt.% To 5 wt.% Of the total monomer mass;
  • R 30 represents H or CH 3 ;
  • R 31 represents a C 2 to C 4 linear alkyl group
  • R 32 , R 33 and R 34 each represent a C 1 to C 4 alkyl group.
  • the cationic monomer is a combination of one or more kinds selected from quaternary ammonium salts or acids of compounds represented by the general formula VI-1, VI-2, VI-3, and the specific structure is as follows:
  • R 35 represents H or CH 3 ;
  • R 36 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
  • R 37 and R 38 represent H, CH 3 , CH 2 CH 3 or
  • R 39 represents H or CH 3 ;
  • R 40 , R 42 and R 43 represent H, CH 3 , CH 2 CH 3 or
  • R 41 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
  • R 44 represents H, CH 3 , CH 2 CH 3 or
  • the compounds represented by the above general formulas VI-1, VI-2, VI-3 need to pass through methyl chloride, ethyl chloride, benzyl chloride, allyl chloride, dimethyl sulfate, diethyl sulfate or epichlorohydrin. Use after forming a quaternary ammonium salt, or use it after reacting with an inorganic or organic acid;
  • the anionic monomer is a compound represented by the general formula VII-1, VII-2, VII-3, VII-4, VII-5, or VII-6, and the specific structure is as follows:
  • R 47 represents H, CH 3 or CH 2 COOH
  • R 48 and R 49 represent H, CH 3 , CH 2 CH 3 or
  • R 50 represents H or CH 3 ;
  • R 51 represents H or CH 3 ;
  • R 52 represents H, CH 3 , CH 2 CH 3 or
  • R 53 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
  • R 54 represents H or CH 3 ;
  • R 55 represents H or CH 3 ;
  • the mass ratio of the six types of monomers in the water-soluble solid polyacrylamide and the copolymer of the solid polyacrylamide is:
  • Non-ionic monomer A 40-90wt%
  • Non-ionic monomer B 1-30wt%
  • Crosslinking agent 0.005-0.2wt%
  • Modified monomer 0.2-5wt%
  • Cationic monomer 1-30wt%
  • Anionic monomer 0.3-30 wt%.
  • the water-soluble solid polyacrylamide is in the form of a solid product, and the particle diameter of the solid polyacrylamide is less than 5 mm, preferably less than 2 mm.
  • the molecular weight of the solid polyacrylamide is from 100,000 to 2 million (weight average molecular weight), preferably from 200 to 1.5 million.
  • water-soluble solid polyacrylamide is used as a papermaking enhancer, as the molecular weight rises, it can promote the improvement of water filtration performance, and it can also help improve the strength.
  • the molecular weight of the solid polyacrylamide is from 100,000 to 2 million (weight average molecular weight), and more preferably from 300 to 1 million.
  • the cationic monomer is a quaternary ammonium salt formed after quaternization of a compound represented by the general formula VI-1, VI-2 or VI-3, or the compound and an inorganic acid or organic Use after acid reaction; and / or
  • the anionic monomer is an alkali metal salt, an ammonium salt or an alkaline earth metal salt of a compound represented by the general formula VII-1, VII-2, VII-3, VII-4, VII-5 or VII-6.
  • the water-soluble solid polyacrylamide comprises the non-ionic monomer A, the non-ionic monomer B, the cross-linking agent, the modified monomer, the Cationic monomer and the anionic monomer are prepared by chain polymerization.
  • the chain polymerization is radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization; and / or
  • the chain polymerization is selected from one or more of photoinitiation, thermal decomposition initiation, redox initiation, and radiation initiation.
  • the water-soluble solid polyacrylamide is obtained in an aqueous solution system or a suspension polymerization system.
  • the water-soluble solid polyacrylamide is a liquid, a colloid or a granule obtained in the system, and granules and / or powdery products are obtained after drying and sieving.
  • surfactants inorganic salts, urea, silica, silicone oil, high-boiling hydrocarbon compounds, natural polymer materials, synthetic polymer materials, semi-natural semi-synthetic materials, minerals before and / or after polymerization
  • surfactants inorganic salts, urea, silica, silicone oil, high-boiling hydrocarbon compounds, natural polymer materials, synthetic polymer materials, semi-natural semi-synthetic materials, minerals before and / or after polymerization
  • the high-boiling hydrocarbon mixture includes one or more of saturated hydrocarbons, unsaturated hydrocarbons, and aromatic hydrocarbons;
  • the natural polymer material is selected from the group consisting of fiber, starch, vegetable gum, animal gum, or seaweed gum;
  • the vegetable gum is one of acacia gum, locust bean gum, astragalus gum, guanidine gum, tianjing gum, and soybean gum Or more;
  • the animal glue is one or more of bone glue, gelatin, casein, and chitosan;
  • the seaweed glue is one of sodium alginate, sodium alginate, or agar Multiple
  • the artificially synthesized polymer materials include condensation-type and polymerization-type polymer materials; wherein, the condensation-type polymer materials are selected from one or more of polyamine resin, amino resin, and polyurethane resin; From one or more of polyacrylamide, polyacrylic acid, polyethylene glycol, polyethylene oxide, polymaleic anhydride, polyquaternium;
  • the semi-natural semi-synthetic polymer material includes modified fiber, modified starch, modified cellulose and modified vegetable gum.
  • the mineral material includes one or more of bentonite, modified bentonite, kaolin, zeolite, and diatomaceous earth.
  • the invention also adopts the following technical scheme: the use of the water-soluble solid polyacrylamide in the reinforcement and / or modification of natural fiber materials or semi-synthetic fiber materials in a papermaking system.
  • the water-soluble solid polyacrylamide is used as a papermaking enhancer, as the molecular weight rises, it can promote the improvement of water filtration performance, and it can also help improve the strength.
  • the product cannot be achieved. It also helps to improve retention, water filtration performance, reduce sediments, stickies, etc.
  • the reinforcing effect includes one or more of tensile strength, tearing resistance, burst resistance, ring pressure resistance, folding resistance and surface strength.
  • the present invention adopts the above scheme, and has the following advantages over the prior art:
  • amphoteric polyacrylamide solid form products can be obtained. Compared with traditional amphoteric polyacrylamide liquid products, solid products have the advantages of high effective content, low transportation cost, not easy hydrolysis, not easy to mold, long shelf life, etc. .
  • the amphoteric polyacrylamide solid product of the present invention can reach more than 85% of effective substances, a shelf life of more than one year, and a molecular weight of up to more than 2 million.
  • the preparation process of the amphoteric polyacrylamide solid product of the present invention conforms to the development direction of green environmental protection, energy saving and low carbon, and has a wide range of fields such as papermaking, water treatment, textile printing and dyeing, leather, petroleum, mining, building materials, daily chemical, medicine, agriculture and other fields. Application prospects, especially for natural fiber materials or semi-synthetic fiber materials with reinforcement and / or modification.
  • a novel water-soluble solid amphoteric polyacrylamide was prepared according to the following steps:
  • the chain transfer agent consists of C1-C4 lower fatty alcohol, polyethylene glycol, benzyl alcohol, hypophosphite, formate, alkyl sulfonate, (meth) allyl sulfonate, mercaptoethanol Or one or two or more of alkyl mercaptan and urea; the mass of the chain transfer agent is 0.01 to 2 wt% of the total mass of the monomers.
  • the pH adjusting agent is one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, formic acid, acetic acid, propionic acid, adipic acid, benzoic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate. Or two or more constitutions, the pH adjusting agent is used to control the pH value in the whole reaction system to be between 2.0 and 9.0.
  • the chelating agent is one or more of EDTA-2Na and / or DTPA-5Na, and the mass of the chelating agent is 0.001-0.1 wt% of the total mass of the whole material.
  • the organic solvent is one or more of a linear paraffin, an isoparaffin, an alicyclic hydrocarbon, an aromatic hydrocarbon, petroleum ether, kerosene, and diesel.
  • the organic solvent is preferably cyclohexane, n-hexane, or n-heptane as the preferred organic solvent.
  • HLB 2-12 sorbitol fatty acid esters, mainly including sorbitol distearate, sorbitol tristearate, sorbitol monolaurate, sorbitol monostearate, One or more of sorbitol monooleate and sorbitol monopalmitate.
  • Chain polymerization refers to the rapid chain-growth polymerization initiated by the active center of the monomer. Chain polymerization requires an active center, which can be divided into free radical polymerization, cationic polymerization, anionic polymerization, and coordination polymerization according to the different active centers.
  • the chain polymerization is radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization; and / or
  • the chain polymerization is selected from one or more of photoinitiation, thermal decomposition initiation, redox initiation, and radiation initiation.
  • the photoreaction is achieved by one or more compounds of a photoinitiator and / or an azo initiator; the mass of the photoinitiator is 50 to 1000 ppm of the total mass of all substances in the entire reaction system; The mass of the azo initiator is 0.001 to 0.2 wt% of the total mass of the monomers;
  • the photoinitiator is made of diphenyl (2,4,6-trimethylbenzoyl) phosphonium oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphonium oxide, 2,4, Ethyl 6-trimethylbenzoylphenylphosphonate, benzophenone, 4-methyldimethanone, 2-methyl-1- (4-methylthiophenyl) -2-morpholine -1-Acetone, 1-Hydroxycyclohexylphenylketone, 2-Hydroxy-2-methyl-1-phenyl-1-propanone, 2,2-Dimethoxy-2-phenylacetophenone (Benzoin dimethyl ether), 2-benzyl-2-dimethylamino-1- (4-morpholinyl) butanone, isopropylthioanthrone, methyl benzoylformate, 4-di One or two or more of methylaminobenzoate;
  • the azo initiator is composed of 2,2-azobis (2-fluorenylpropane) dihydrochloride (V-50), 2,2-azobis (2-imidazolinylpropane) dihydrochloride (VA- 044), 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2,4-dimethylvaleronitrile) (ABVN), dimethyl azobisisobutyrate (AIBME ), 2,2′-azo-bis- (2-methylbutyronitrile) (AMBN), 2,2′-azo (2-methyl-N- (2-hydroxyethyl) propionamide) Of one or two or more.
  • the thermal decomposition initiator comprises benzoyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, 2,2-coupling Azobis (2-fluorenylpropane) dihydrochloride (V-50), 2,2-azobis (2-imidazolinylpropane) dihydrochloride (VA-044), 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2,4-dimethylvaleronitrile) (ABVN), dimethyl azobisisobutyrate (AIBME), 2,2′-azo-bis- ( One or two or more of 2-methylbutyronitrile) (AMBN), 2,2'-azo (2-methylN- (2-hydroxyethyl) propionamide).
  • V-50 2,2-coupling Azobis (2-fluorenylpropane) dihydrochloride
  • the redox reaction is achieved by a redox initiator composed of an oxidizing agent and a reducing agent, and the mass of the redox initiator is 0.001 to 0.3% of the mass of the four types of monomers;
  • the oxidant is composed of one or two or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, sodium bromate, and potassium bromate;
  • the reducing agent comprises one or two or more of sodium bisulfite, sodium sulfite, sodium bisulfite, sodium dithionite, ferrous sulfate, ferrous ammonium sulfate, triethylamine, triethanolamine, and tetramethylethylenediamine.
  • the mass ratio of the oxidant to the reducing agent is 1: 3-3: 2.
  • Examples 1-4, 5-8, 9-12, and 13-16 are sequentially prepared by redox initiation, thermal initiation, photoinitiation, and radiation initiation, respectively.
  • Table 1 Table 2, Table 3, Table 4.
  • the molecular weight detection methods are as follows:
  • the weight average molecular weight (M W ) was measured by gel permeation chromatography (GPC), and the weight average molecular weight was obtained from the chromatogram.
  • GPC gel permeation chromatography
  • an aqueous polyacrylamide product is prepared:
  • the test was carried out by using a recycled paperboard pulp from a paper mill. The degree of decomposition was 40 ° SR. An aqueous solution of a cross-linked modified amphoteric polyacrylamide was added to the pulp, stirred for 10 minutes, and copied. Amphoteric polyacrylamide is added in an amount of 2.0 to 6 kg / t (the amount after deducting moisture based on the solid content of the product). After being formed by a paper shaper, it is pressed by a standard paper press, dried at 100 to 105 ° C, and then tested for strength properties such as breakage resistance, tensile strength, ring pressure, folding resistance, internal bonding, etc., and tested for water filtration. performance. Table 6 shows the application data of the reinforcing effect of the cross-linked modified water-soluble solid polyacrylamide prepared by the above method on the paper and its effect on the water filtration performance.
  • Examples 17-20 are the preparation of a water-soluble amphoteric polyacrylamide solid product by the polymerization initiation method adopted in the present invention, as shown in Table 7.
  • Examples 21 and 22 are prepared by using the polymerization initiation method of the present invention to prepare a water-soluble amphoteric polyacrylamide solid product.

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Abstract

A crosslinking modified type water-soluble solid polyacrylamide. The crosslinking modified type water-soluble solid polyacrylamide is at least formed by means of the chain polymerization and copolymerization of six kinds of monomers, such as a nonionic monomer A, a nonionic monomer B, a crosslinking agent, a modifying monomer, a cationic monomer, and an anionic monomer. The present invention resolves the problems existing in a water-soluble type amphoteric polyacrylamide product that the molecular weight is low, the content of an effective substance is low, storage stability is poor, and shelf life is short; a higher molecular weight product can be obtained, wherein the content of the effective substance is high, transportation costs are low, and the product is not easy to hydrolyze and mildew. The crosslinking modified type water-soluble solid polyacrylamide can be used for the enhancement and/or modification of a natural fiber material or a semi-synthetic fiber material, promotes the improvement of drainage performance, and also helps strength enhancement.

Description

一种交联改性型水溶性固体聚丙烯酰胺及其用途Crosslinked modified water-soluble solid polyacrylamide and use thereof 技术领域Technical field
本发明属于水溶性高分子材料领域，具体涉及一种交联改性型水溶性固体聚丙烯酰胺及其用途。The invention belongs to the field of water-soluble polymer materials, and particularly relates to a cross-linked modified water-soluble solid polyacrylamide and use thereof.
背景技术Background technique
聚丙烯酰胺作为优良的工业助剂按照产品状态可分为：水溶液型、乳液型、固体型(或称为粉剂型)三大类。按其带电性可分为阳离子聚丙烯酰胺、阴离子聚丙烯酰胺、非离子聚丙烯酰胺和两性聚丙烯酰胺，两性聚丙烯酰胺由于其分子中同时含有阴、阳离子基团使其应用范围变的越来越广泛，与含有单一的阴离子基团或阳离子基团聚丙烯酰胺相比，不仅同时具备二者的综合性能，而且有明显的反聚电解质效应和pH适应范围广等特点，这些性能与特点为两性聚丙烯酰胺的广泛应用提供了有力支撑。Polyacrylamide as an excellent industrial additive can be divided into three types: aqueous solution type, emulsion type, and solid type (or called powder type) according to the product status. According to its chargeability, it can be divided into cationic polyacrylamide, anionic polyacrylamide, nonionic polyacrylamide, and amphoteric polyacrylamide. Amphoteric polyacrylamide has an anionic and cationic group in its molecule, which makes its application range more and more. Compared with polyacrylamide containing a single anionic group or cationic group, it not only has the comprehensive properties of the two at the same time, but also has obvious anti-polyelectrolyte effect and a wide range of pH adaptation. These properties and characteristics are The extensive application of amphoteric polyacrylamide provides strong support.
目前市场上的水溶液型两性聚丙烯酰胺产品在造纸中用于纸页增强作用，效果明显，尤其在提升二次回用纤维增强中应用非常广泛。但是水溶液型两性聚丙烯酰胺产品也存在如下问题：一、分子量低，大多在30万-60万，如果需要获得更高分子量的产品，那其水溶液粘度会随分子量升高而升高，影响产品流动性，并进而影响使用(液体输送与溶解都变得困难)；水溶液产品固含量低，市场上基本是在15％-20％左右，超过25％的非常少见，提高含量的话，粘度也会上升，影响使用。二、两性聚丙烯酰胺液体产品由于含有大量水分，产品存储过程中易发霉变质，同时，其分子结构中的酯基容易水解，导致聚合物分子结构变化，影响使用效果。三、两性聚丙烯酰胺液体产品，由于固含量低，导致运输成本高、包装成本高。四、两性聚丙烯酰胺液体产品保质期短，大多数产品实际保质期只有三个月，最长不超过六个月。At present, the aqueous solution amphoteric polyacrylamide products on the market are used to strengthen the sheet in papermaking, and the effect is obvious. Especially, it is widely used to enhance the secondary reuse fiber reinforcement. However, the water-based amphoteric polyacrylamide products also have the following problems: First, the molecular weight is low, mostly between 300,000 and 600,000. If higher molecular weight products are needed, the viscosity of the aqueous solution will increase as the molecular weight increases, affecting the product. Flowability, which further affects the use (liquid transportation and dissolution become difficult); the solid content of aqueous products is low, which is basically around 15% -20% on the market, exceeding 25% is very rare. If the content is increased, the viscosity will also be Rise and affect use. Second, because amphoteric polyacrylamide liquid products contain a large amount of water, the product is prone to mildew during storage. At the same time, the ester group in its molecular structure is easily hydrolyzed, resulting in changes in the molecular structure of the polymer and affecting the use effect. Third, amphoteric polyacrylamide liquid products, due to the low solid content, lead to high transportation costs and high packaging costs. 4. Shelf life of amphoteric polyacrylamide liquid products is short. The actual shelf life of most products is only three months, and the longest is no more than six months.
如徐娘，胡惠仁公开了以丙烯酰胺、甲基丙烯酰氧乙基三甲基氯化铵、丙烯酸、N-羟甲基丙烯酰胺为主要原料制备聚丙烯酰胺，在15％、20％有效含量下的水溶液聚合反应，20％情况下反应升温剧烈(参见：AmPAM纸张干强剂生产过程的温度控制[J]中国造纸，2014，33(12)：19-23))。Such as Xu Niang, Hu Huiren disclosed the preparation of polyacrylamide with acrylamide, methacryloyloxyethyltrimethylammonium chloride, acrylic acid, and N-methylol acrylamide as main raw materials. Under the condition of aqueous solution polymerization reaction, the reaction temperature rises sharply at 20% (see: Temperature control in the production process of AmPAM paper dry strength agent [J] China Papermaking, 2014, 33 (12): 19-23).
中国专利CN107366182A公开了一种丙烯酰胺系聚合物，其为如下聚合成分的聚合物，聚合成分含有(甲基)丙烯酰胺、季铵系单体和(甲基)烯丙基磺酸盐，且不含含氮交联性单体和叔胺基系单体。Chinese patent CN107366182A discloses an acrylamide polymer, which is a polymer of a polymerization component including a (meth) acrylamide, a quaternary ammonium monomer, and a (meth) allyl sulfonate, and Does not contain nitrogen-containing crosslinkable monomers and tertiary amino-based monomers.
上述文献和专利中，制得的聚丙烯酰胺为水溶液型，有效物含量低，运输成本高，易水解。In the above documents and patents, the prepared polyacrylamide is an aqueous solution type with low effective content, high transportation cost, and easy hydrolysis.
发明内容Summary of the invention
本发明的目的是提供一种交联改性型水溶性固体聚丙烯酰胺产品，以解决水溶液型两性聚丙烯酰胺产品存在的分子量低、有效物含量低、存储稳定性差、保质期短等问题，可获得更高分子量产品，有效 物含量高，运输成本低，不易水解，不易发霉。本发明还提供所述水溶性固体聚丙烯酰在天然纤维材料或者半合成纤维材料的增强和/或改性中的用途。The purpose of the present invention is to provide a cross-linked modified water-soluble solid polyacrylamide product, which can solve the problems of low molecular weight, low effective content, poor storage stability, short shelf life, and the like of the aqueous type amphoteric polyacrylamide product. Obtain higher molecular weight products, high effective content, low transportation cost, not easy to hydrolyze, not easy to mold. The invention also provides the use of the water-soluble solid polyacryl in the reinforcement and / or modification of natural fiber materials or semi-synthetic fiber materials.
本发明采用如下技术方案：所述的一种水溶性固体聚丙烯酰胺，水溶性固体聚丙烯酰胺至少由非离子单体A、非离子单体B、交联剂、改性单体、阳离子单体以及阴离子单体六类单体连锁聚合共聚而成，所述的六类单体的其结构通式如下：The present invention adopts the following technical scheme: The said water-soluble solid polyacrylamide is composed of at least a nonionic monomer A, a nonionic monomer B, a crosslinking agent, a modified monomer, and a cationic monomer. And anionic monomers are obtained by chain polymerization of six types of monomers. The structure of the six types of monomers is as follows:
所述的非离子单体A，其结构通式I如下：The structure of the non-ionic monomer A is as follows:
Figure PCTCN2018093383-appb-000001
Figure PCTCN2018093383-appb-000001
其中：R 1表示H或CH 3； Wherein: R 1 represents H or CH 3 ;
R 2和R 3表示H，CH 3，CH 2CH 3或
Figure PCTCN2018093383-appb-000002
R 2 and R 3 represent H, CH 3 , CH 2 CH 3 or
Figure PCTCN2018093383-appb-000002
所述的非离子单体B，选自如下结构通式II-1、II-2、II-3所示化合物中的一种或多种的组合：The non-ionic monomer B is selected from a combination of one or more of the compounds represented by the following general formula II-1, II-2, and II-3:
Figure PCTCN2018093383-appb-000003
Figure PCTCN2018093383-appb-000003
其中：R 4表示H或CH 3； Wherein: R 4 represents H or CH 3 ;
R 5表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
Figure PCTCN2018093383-appb-000004
R 5 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
Figure PCTCN2018093383-appb-000004
R 6和R 7表示H，CH 3，CH 2CH 3或
Figure PCTCN2018093383-appb-000005
R 6 and R 7 represent H, CH 3 , CH 2 CH 3 or
Figure PCTCN2018093383-appb-000005
Figure PCTCN2018093383-appb-000006
Figure PCTCN2018093383-appb-000006
其中：among them:
R 8表示H或CH 3； R 8 represents H or CH 3 ;
R 9和R 11、R 12表示H，CH 3，CH 2CH 3或
Figure PCTCN2018093383-appb-000007
R 9 and R 11 and R 12 represent H, CH 3 , CH 2 CH 3 or
Figure PCTCN2018093383-appb-000007
R 10表示CH 2，CH 2CH 2、CH 2CH 2CH 2或
Figure PCTCN2018093383-appb-000008
R 10 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
Figure PCTCN2018093383-appb-000008
Figure PCTCN2018093383-appb-000009
Figure PCTCN2018093383-appb-000009
其中：among them:
R 13表示H或CH 3； R 13 represents H or CH 3 ;
R 14表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
Figure PCTCN2018093383-appb-000010
R 14 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
Figure PCTCN2018093383-appb-000010
R 15和R 16表示H，CH 3，CH 2CH 3或
Figure PCTCN2018093383-appb-000011
R 15 and R 16 represent H, CH 3 , CH 2 CH 3 or
Figure PCTCN2018093383-appb-000011
所述的交联剂，其结构通式如下式III-1、III-2、III-3、III-4、III-5、III-6、或III-7：The cross-linking agent has a general structural formula of the following formula III-1, III-2, III-3, III-4, III-5, III-6, or III-7:
1)双丙烯酰胺：1) Bisacrylamide:
Figure PCTCN2018093383-appb-000012
Figure PCTCN2018093383-appb-000012
2)三烯丙基胺：2) Triallylamine:
Figure PCTCN2018093383-appb-000013
Figure PCTCN2018093383-appb-000013
3)双丙烯酸酯：3) Diacrylate:
Figure PCTCN2018093383-appb-000014
Figure PCTCN2018093383-appb-000014
4)三丙烯酸酯：4) Triacrylate:
Figure PCTCN2018093383-appb-000015
Figure PCTCN2018093383-appb-000015
其中：among them:
R 17表示OH或CH 3； R 17 represents OH or CH 3 ;
R 18、R 19和R 20表示
Figure PCTCN2018093383-appb-000016
R 18 , R 19 and R 20 represent
Figure PCTCN2018093383-appb-000016
5)三烯丙基型：5) Triallyl type:
Figure PCTCN2018093383-appb-000017
Figure PCTCN2018093383-appb-000017
其中：among them:
R 21、R 22和R 23表示CH 2或CH 2CH 2； R 21 , R 22 and R 23 represent CH 2 or CH 2 CH 2 ;
6)四乙烯基型：6) Tetravinyl type:
Figure PCTCN2018093383-appb-000018
Figure PCTCN2018093383-appb-000018
其中：among them:
R 24、R 25、R 26、R 27表示CH 2、CH 2CH 2。 R 24 , R 25 , R 26 , and R 27 represent CH 2 and CH 2 CH 2 .
所述的改性单体包括改性单体A、改性单体B中的一种或两种；The modified monomer includes one or two of modified monomer A and modified monomer B;
所述的改性单体A包含(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、丙烯腈、羟甲基丙烯酰胺、苯乙烯、乙烯基吡咯烷酮、4-乙烯基吡啶、(甲基)丙烯酸酯类单体中的一种或多种；The modified monomer A includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, acrylonitrile, hydroxymethacrylamide, styrene, vinylpyrrolidone, 4 -One or more of vinylpyridine and (meth) acrylate monomers;
所述的(甲基)丙烯酸酯类单体的结构通式IV如下：The structural formula IV of the (meth) acrylate monomer is as follows:
Figure PCTCN2018093383-appb-000019
Figure PCTCN2018093383-appb-000019
其中：R 28表示H或CH 3； Wherein: R 28 represents H or CH 3 ;
R 29表示H，CH 3，(CH 2) nCH 3，n≤6(n为整数)。 R 29 represents H, CH 3 , (CH 2 ) n CH 3 , and n ≦ 6 (n is an integer).
所述的改性单体B为有机硅单体，具体包括3-(N-烯丙基氨基)丙基三甲氧基硅烷、二甲基(二 甲胺基)乙烯基硅烷、烯丙基(二异丙基氨基)二甲基硅烷、乙烯基-三(2-甲氧基乙氧基)硅烷、烯丙基三甲氧基硅烷或结构通式(V)表示的化合物中的一种或两种及两种以上形成的混合物，其用量为总单体质量的0.5wt.％～5wt.％；The modified monomer B is an organic silicon monomer, and specifically includes 3- (N-allylamino) propyltrimethoxysilane, dimethyl (dimethylamino) vinylsilane, allyl ( One or two of diisopropylamino) dimethylsilane, vinyl-tris (2-methoxyethoxy) silane, allyltrimethoxysilane, or a compound represented by the general formula (V) Species and a mixture of two or more species in an amount of 0.5 wt.% To 5 wt.% Of the total monomer mass;
所述的结构通式(V)为：The structural formula (V) is:
Figure PCTCN2018093383-appb-000020
Figure PCTCN2018093383-appb-000020
其中：R 30表示H或CH 3； Wherein: R 30 represents H or CH 3 ;
R 31表示C 2～C 4的直链烷基； R 31 represents a C 2 to C 4 linear alkyl group;
R 32、R 33、R 34表示C 1～C 4的烷基。 R 32 , R 33 and R 34 each represent a C 1 to C 4 alkyl group.
所述的阳离子单体为选自结构通式VI-1、VI-2、VI-3所示的化合物的季铵盐或酸中的一种或多种的组合，具体结构如下：The cationic monomer is a combination of one or more kinds selected from quaternary ammonium salts or acids of compounds represented by the general formula VI-1, VI-2, VI-3, and the specific structure is as follows:
Figure PCTCN2018093383-appb-000021
Figure PCTCN2018093383-appb-000021
其中：R 35表示H或CH 3； Wherein: R 35 represents H or CH 3 ;
R 36表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
Figure PCTCN2018093383-appb-000022
R 36 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
Figure PCTCN2018093383-appb-000022
R 37、R 38表示H，CH 3，CH 2CH 3或
Figure PCTCN2018093383-appb-000023
R 37 and R 38 represent H, CH 3 , CH 2 CH 3 or
Figure PCTCN2018093383-appb-000023
Figure PCTCN2018093383-appb-000024
Figure PCTCN2018093383-appb-000024
其中：among them:
R 39表示H或CH 3； R 39 represents H or CH 3 ;
R 40、R 42和R 43表示H，CH 3，CH 2CH 3或
Figure PCTCN2018093383-appb-000025
R 40 , R 42 and R 43 represent H, CH 3 , CH 2 CH 3 or
Figure PCTCN2018093383-appb-000025
R 41表示CH 2，CH 2CH 2、CH 2CH 2CH 2或
Figure PCTCN2018093383-appb-000026
R 41 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
Figure PCTCN2018093383-appb-000026
Figure PCTCN2018093383-appb-000027
Figure PCTCN2018093383-appb-000027
其中：among them:
R 44表示H，CH 3，CH 2CH 3或
Figure PCTCN2018093383-appb-000028
R 44 represents H, CH 3 , CH 2 CH 3 or
Figure PCTCN2018093383-appb-000028
上述结构通式VI-1、VI-2、VI-3表示的化合物需经氯甲烷、氯乙烷、氯化苄、烯丙基氯、硫酸二甲酯、硫酸二乙酯或环氧氯丙烷形成季铵盐后使用，也可以与无机酸或有机酸反应后使用；The compounds represented by the above general formulas VI-1, VI-2, VI-3 need to pass through methyl chloride, ethyl chloride, benzyl chloride, allyl chloride, dimethyl sulfate, diethyl sulfate or epichlorohydrin. Use after forming a quaternary ammonium salt, or use it after reacting with an inorganic or organic acid;
所述的阴离子单体为结构通式VII-1、VII-2、VII-3、VII-4、VII-5或VII-6所示的化合物或其盐，具体结构如下：The anionic monomer is a compound represented by the general formula VII-1, VII-2, VII-3, VII-4, VII-5, or VII-6, and the specific structure is as follows:
Figure PCTCN2018093383-appb-000029
Figure PCTCN2018093383-appb-000029
其中：among them:
R 47表示H，CH 3或CH 2COOH； R 47 represents H, CH 3 or CH 2 COOH;
Figure PCTCN2018093383-appb-000030
Figure PCTCN2018093383-appb-000030
其中：among them:
R 48和R 49表示H，CH 3，CH 2CH 3或
Figure PCTCN2018093383-appb-000031
R 48 and R 49 represent H, CH 3 , CH 2 CH 3 or
Figure PCTCN2018093383-appb-000031
Figure PCTCN2018093383-appb-000032
Figure PCTCN2018093383-appb-000032
其中：among them:
R 50表示H或CH 3； R 50 represents H or CH 3 ;
Figure PCTCN2018093383-appb-000033
Figure PCTCN2018093383-appb-000033
其中：among them:
R 51表示H或CH 3； R 51 represents H or CH 3 ;
R 52表示H，CH 3，CH 2CH 3或
Figure PCTCN2018093383-appb-000034
R 52 represents H, CH 3 , CH 2 CH 3 or
Figure PCTCN2018093383-appb-000034
R 53表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
Figure PCTCN2018093383-appb-000035
R 53 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
Figure PCTCN2018093383-appb-000035
Figure PCTCN2018093383-appb-000036
Figure PCTCN2018093383-appb-000036
其中：R 54表示H或CH 3； Wherein: R 54 represents H or CH 3 ;
Figure PCTCN2018093383-appb-000037
Figure PCTCN2018093383-appb-000037
其中：R 55表示H或CH 3； Wherein: R 55 represents H or CH 3 ;
上述结构通式VII-1、VII-2、VII-3、VII-4、VII-5或VII-6所示的化合物的碱金属盐、铵盐或碱土金属盐，具体为其中的磺酸基、羧基、瞵酸基的碱金属盐、铵盐或碱土金属盐。Alkali metal salt, ammonium salt or alkaline earth metal salt of the compound represented by the above general formula VII-1, VII-2, VII-3, VII-4, VII-5 or VII-6, specifically sulfonic acid group , Carboxyl, phosphonate, alkali metal, ammonium or alkaline earth metal salts.
所述的水溶性固体聚丙烯酰胺，所述的固体聚丙烯酰胺的共聚物中六类单体质量比为：The mass ratio of the six types of monomers in the water-soluble solid polyacrylamide and the copolymer of the solid polyacrylamide is:
非离子单体A：40-90wt％；Non-ionic monomer A: 40-90wt%;
非离子单体B：1-30wt％；Non-ionic monomer B: 1-30wt%;
交联剂：0.005-0.2wt％；Crosslinking agent: 0.005-0.2wt%;
改性单体：0.2-5wt％；Modified monomer: 0.2-5wt%;
阳离子单体：1-30wt％；Cationic monomer: 1-30wt%;
阴离子单体：0.3-30wt％。Anionic monomer: 0.3-30 wt%.
所述的水溶性固体聚丙烯酰胺，所述的固体聚丙烯酰胺为固体产品形式，其颗粒粒径小于5mm，优选地，小于2mm。The water-soluble solid polyacrylamide is in the form of a solid product, and the particle diameter of the solid polyacrylamide is less than 5 mm, preferably less than 2 mm.
所述的水溶性固体聚丙烯酰胺，所述的固体聚丙烯酰胺分子量为10万-200万(重均分子量)，优选20-150万。水溶性固体聚丙烯酰胺用于造纸增强剂时，随着分子量上升，其对滤水性能的改善是有促进作用的，而且对强度提升也有帮助。In the water-soluble solid polyacrylamide, the molecular weight of the solid polyacrylamide is from 100,000 to 2 million (weight average molecular weight), preferably from 200 to 1.5 million. When water-soluble solid polyacrylamide is used as a papermaking enhancer, as the molecular weight rises, it can promote the improvement of water filtration performance, and it can also help improve the strength.
所述的固体聚丙烯酰胺分子量为10万-200万(重均分子量)，更优选30-100万。The molecular weight of the solid polyacrylamide is from 100,000 to 2 million (weight average molecular weight), and more preferably from 300 to 1 million.
所述的水溶性固体聚丙烯酰胺，所述阳离子单体为通式VI-1，VI-2或VI-3所示的化合物季铵化后形成的季铵盐或该化合物与无机酸或有机酸反应后使用；和/或In the water-soluble solid polyacrylamide, the cationic monomer is a quaternary ammonium salt formed after quaternization of a compound represented by the general formula VI-1, VI-2 or VI-3, or the compound and an inorganic acid or organic Use after acid reaction; and / or
所述阴离子单体为通式VII-1，VII-2，VII-3，VII-4，VII 5或VII-6所示的化合物的碱金属盐、铵盐或碱土金属盐。The anionic monomer is an alkali metal salt, an ammonium salt or an alkaline earth metal salt of a compound represented by the general formula VII-1, VII-2, VII-3, VII-4, VII-5 or VII-6.
所述的水溶性固体聚丙烯酰胺，所述水溶性固体聚丙烯酰胺由所述非离子单体A、所述非离子单体B、所述交联剂、所述改性单体、所述阳离子单体以及所述阴离子单体连锁聚合制得。The water-soluble solid polyacrylamide comprises the non-ionic monomer A, the non-ionic monomer B, the cross-linking agent, the modified monomer, the Cationic monomer and the anionic monomer are prepared by chain polymerization.
所述连锁聚合为自由基聚合、阴离子聚合、阳离子聚合或配位聚合；和/或The chain polymerization is radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization; and / or
所述的连锁聚合选用光引发、热分解引发、氧化还原引发、辐射引发中的一种或多种。The chain polymerization is selected from one or more of photoinitiation, thermal decomposition initiation, redox initiation, and radiation initiation.
所述的水溶性固体聚丙烯酰胺在水溶液体系或者悬浮聚合体系中获得。The water-soluble solid polyacrylamide is obtained in an aqueous solution system or a suspension polymerization system.
所述的水溶性固体聚丙烯酰胺为在体系中获得的液体、胶体或颗粒，并经过干燥、筛分后制得颗粒和/或粉状产品。The water-soluble solid polyacrylamide is a liquid, a colloid or a granule obtained in the system, and granules and / or powdery products are obtained after drying and sieving.
在聚合前和/或聚合后加入表面活性剂、无机盐、尿素、二氧化硅、硅油、高沸点烃类化合物、天然高分子材料、人工合成的高分子材料、半天然半人工合成材料、矿物材料中的一种或多种；Add surfactants, inorganic salts, urea, silica, silicone oil, high-boiling hydrocarbon compounds, natural polymer materials, synthetic polymer materials, semi-natural semi-synthetic materials, minerals before and / or after polymerization One or more of the materials;
所述的高沸点烃类混合物包括饱和烃、不饱和烃和芳香烃中的一种或多种；The high-boiling hydrocarbon mixture includes one or more of saturated hydrocarbons, unsaturated hydrocarbons, and aromatic hydrocarbons;
所述的天然高分子材料选自纤维、淀粉、植物胶、动物胶或海藻胶；所述植物胶为阿拉伯胶、槐豆胶、黄芪胶、胍胶、田菁胶、大豆胶中的一种或多种；所述的动物胶为骨胶、明胶、干酪素、壳聚糖中的一种或多种；所述的海藻胶为藻蛋白酸钠、海藻酸钠、琼胶中的一种或多种；The natural polymer material is selected from the group consisting of fiber, starch, vegetable gum, animal gum, or seaweed gum; the vegetable gum is one of acacia gum, locust bean gum, astragalus gum, guanidine gum, tianjing gum, and soybean gum Or more; the animal glue is one or more of bone glue, gelatin, casein, and chitosan; the seaweed glue is one of sodium alginate, sodium alginate, or agar Multiple
所述人工合成的高分子材料包括缩合类和聚合类高分子材料；其中，缩合类高分子材料选自聚胺树脂、氨基树脂和聚氨酯树脂中的一种或多种；聚合类高分子材料选自聚丙烯酰胺、聚丙烯酸、聚乙二醇、聚氧化乙烯、聚马来酸酐、聚季铵盐中的一种或多种；The artificially synthesized polymer materials include condensation-type and polymerization-type polymer materials; wherein, the condensation-type polymer materials are selected from one or more of polyamine resin, amino resin, and polyurethane resin; From one or more of polyacrylamide, polyacrylic acid, polyethylene glycol, polyethylene oxide, polymaleic anhydride, polyquaternium;
所述的半天然半人工合成的高分子材料包括改性纤维、改性淀粉、改性纤维素和改性植物胶。The semi-natural semi-synthetic polymer material includes modified fiber, modified starch, modified cellulose and modified vegetable gum.
所述的矿物材料包括膨润土、改性膨润土、高岭土、沸石、硅藻土中的一种或多种。The mineral material includes one or more of bentonite, modified bentonite, kaolin, zeolite, and diatomaceous earth.
本发明还采用如下技术方案：所述的水溶性固体聚丙烯酰胺在造纸系统中的天然纤维材料或半合成纤维材料增强和/或改性中的用途。当所述的水溶性固体聚丙烯酰胺用于造纸增强剂时，随着分子量上升，其对滤水性能的改善是有促进作用的，而且对强度提升也有帮助，这是水溶液形式的聚丙烯酰胺产品无法实现的。还有助于提升保留率、滤水性能、减少沉积物、胶黏物等。The invention also adopts the following technical scheme: the use of the water-soluble solid polyacrylamide in the reinforcement and / or modification of natural fiber materials or semi-synthetic fiber materials in a papermaking system. When the water-soluble solid polyacrylamide is used as a papermaking enhancer, as the molecular weight rises, it can promote the improvement of water filtration performance, and it can also help improve the strength. The product cannot be achieved. It also helps to improve retention, water filtration performance, reduce sediments, stickies, etc.
所述的增强作用包括抗张、撕裂、耐破、环压、耐折、表面强度等中的一种或多种。The reinforcing effect includes one or more of tensile strength, tearing resistance, burst resistance, ring pressure resistance, folding resistance and surface strength.
技术效果Technical effect
本发明采用以上方案，相比现有技术具有如下优点：The present invention adopts the above scheme, and has the following advantages over the prior art:
可以获得较高分子量的水溶性两性聚丙烯酰胺的固体形式产品，相对于传统的两性聚丙烯酰胺液体产品，固体产品具有有效物含量高，运输成本低，不易水解，不易发霉，保质期长等优点。本发明的两 性聚丙烯酰胺固体产品有效物可达85％以上，保质期可达一年以上，分子量最高可达200万以上。本发明的两性聚丙烯酰胺固体产品其制备过程符合绿色环保、节能低碳的发展方向，在造纸、水处理、纺织印染、皮革、石油、采矿、建材、日化、医药、农业等领域有广泛的应用前景，尤其是对天然纤维材料或者半合成纤维材料具有增强和/或改性作用。Higher molecular weight water-soluble amphoteric polyacrylamide solid form products can be obtained. Compared with traditional amphoteric polyacrylamide liquid products, solid products have the advantages of high effective content, low transportation cost, not easy hydrolysis, not easy to mold, long shelf life, etc. . The amphoteric polyacrylamide solid product of the present invention can reach more than 85% of effective substances, a shelf life of more than one year, and a molecular weight of up to more than 2 million. The preparation process of the amphoteric polyacrylamide solid product of the present invention conforms to the development direction of green environmental protection, energy saving and low carbon, and has a wide range of fields such as papermaking, water treatment, textile printing and dyeing, leather, petroleum, mining, building materials, daily chemical, medicine, agriculture and other fields. Application prospects, especially for natural fiber materials or semi-synthetic fiber materials with reinforcement and / or modification.
具体实施方式detailed description
下面对本发明的较佳实施例进行详细阐述，以使本发明的优点和特征能更易于被本领域的技术人员理解。在此需要说明的是，对于这些实施方式的说明用于帮助理解本发明，但并不构成对本发明的限定。此外，下面所描述的本发明各个实施方式中所涉及到的技术特征只要彼此之间未构成冲突就可以互相结合。The preferred embodiments of the present invention are described in detail below, so that the advantages and features of the present invention can be more easily understood by those skilled in the art. It should be noted that the description of these embodiments is used to help understand the present invention, but does not limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not conflict with each other.
根据下述步骤制得新型水溶性固体两性聚丙烯酰胺：A novel water-soluble solid amphoteric polyacrylamide was prepared according to the following steps:
(1)均匀混合链转移剂、pH调节剂、螯合剂、水和/或有机溶剂及表面活性剂形成混合液；(1) uniformly mixing a chain transfer agent, a pH adjuster, a chelating agent, water and / or an organic solvent and a surfactant to form a mixed solution;
(2)将非离子单体A、非离子单体B、交联剂、改性单体、阴离子单体以及阳离子单体置于混合液中，通过惰性气体对其除氧；(2) Put non-ionic monomer A, non-ionic monomer B, cross-linking agent, modified monomer, anionic monomer and cationic monomer in the mixed liquid, and remove oxygen by inert gas;
(3)施加引发条件进行连锁聚合，在水溶液体系或者悬浮体系中获得水溶性聚丙烯酰胺聚合物，所获得的聚合物为液体状、或胶体状、或颗粒状，该聚合物经过干燥、筛分等加工手段成为颗粒状和/或粉状水溶性固体聚丙烯酰胺产品。(3) Initiating conditions for chain polymerization, and obtaining a water-soluble polyacrylamide polymer in an aqueous solution system or a suspension system. The obtained polymer is liquid, or colloidal, or granular, and the polymer is dried and sieved. Grading processing means granulated and / or powdered water-soluble solid polyacrylamide products.
所述链转移剂由C1-C4的低级脂肪醇、聚乙二醇、苄基醇、次磷酸盐、甲酸盐、烷基磺酸盐、(甲基)烯丙基磺酸盐、巯基乙醇或烷基硫醇、尿素中的一种或两种或多种构成；所述链转移剂的质量为所述单体总质量的0.01～2wt％。The chain transfer agent consists of C1-C4 lower fatty alcohol, polyethylene glycol, benzyl alcohol, hypophosphite, formate, alkyl sulfonate, (meth) allyl sulfonate, mercaptoethanol Or one or two or more of alkyl mercaptan and urea; the mass of the chain transfer agent is 0.01 to 2 wt% of the total mass of the monomers.
所述的pH调节剂由盐酸、硫酸、磷酸、硝酸、柠檬酸、甲酸、乙酸、丙酸、己二酸、苯甲酸、氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠中的一种或两种或多种构成，所述的pH调节剂用于控制整个反应体系中的pH值，使其在2.0～9.0之间。The pH adjusting agent is one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, formic acid, acetic acid, propionic acid, adipic acid, benzoic acid, sodium hydroxide, potassium hydroxide, sodium carbonate, and sodium bicarbonate. Or two or more constitutions, the pH adjusting agent is used to control the pH value in the whole reaction system to be between 2.0 and 9.0.
所述的螯合剂为EDTA-2Na和/或DTPA-5Na中的一种或多种，所述螯合剂的质量为整个物料总质量的0.001-0.1wt％。The chelating agent is one or more of EDTA-2Na and / or DTPA-5Na, and the mass of the chelating agent is 0.001-0.1 wt% of the total mass of the whole material.
所述的有机溶剂为直链烷烃、异链烷烃、脂环族烃、芳香族烃、石油醚、煤油、柴油中的一种或多种。The organic solvent is one or more of a linear paraffin, an isoparaffin, an alicyclic hydrocarbon, an aromatic hydrocarbon, petroleum ether, kerosene, and diesel.
所述的有机溶剂，优选环己烷、正己烷、正庚烷作为优选的有机溶剂。The organic solvent is preferably cyclohexane, n-hexane, or n-heptane as the preferred organic solvent.
所述的表面活性剂为HLB＝2～12的山梨糖醇脂肪酸酯。HLB＝2～12的山梨糖醇脂肪酸酯，主要包括山梨糖醇二硬脂酸酯、山梨糖醇三硬脂酸酯、山梨糖醇单月桂酸酯、山梨糖醇单硬脂酸酯、山梨糖醇单油酸酯、山梨糖醇单棕桐酸酯中的一种或多种。The surfactant is a sorbitol fatty acid ester with HLB = 2-12. HLB = 2-12 sorbitol fatty acid esters, mainly including sorbitol distearate, sorbitol tristearate, sorbitol monolaurate, sorbitol monostearate, One or more of sorbitol monooleate and sorbitol monopalmitate.
连锁聚合是指通过活性中心引发单体，迅速连锁增长的聚合。连锁聚合需活性中心，根据活性中心的不同可分为自由基聚合、阳离子聚合、阴离子聚合和配位聚合。所述连锁聚合为自由基聚合、阴离子聚合、阳离子聚合或配位聚合；和/或Chain polymerization refers to the rapid chain-growth polymerization initiated by the active center of the monomer. Chain polymerization requires an active center, which can be divided into free radical polymerization, cationic polymerization, anionic polymerization, and coordination polymerization according to the different active centers. The chain polymerization is radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization; and / or
所述的连锁聚合选用光引发、热分解引发、氧化还原引发、辐射引发中的一种或多种。The chain polymerization is selected from one or more of photoinitiation, thermal decomposition initiation, redox initiation, and radiation initiation.
所述光反应是通过光引发剂和/或偶氮类引发剂中的一种或多种复合来实现的；所述光引发剂的质量为整个反应体系中所有物质总质量的50～1000ppm；所述偶氮类引发剂的质量为所述单体总质量的0.001～0.2wt％；The photoreaction is achieved by one or more compounds of a photoinitiator and / or an azo initiator; the mass of the photoinitiator is 50 to 1000 ppm of the total mass of all substances in the entire reaction system; The mass of the azo initiator is 0.001 to 0.2 wt% of the total mass of the monomers;
所述光引发剂由二苯基(2，4，6-三甲基苯甲酰基)氧化瞵、苯基双(2，4，6-三甲基苯甲酰基)氧化瞵、2，4，6-三甲基苯甲酰基苯基瞵酸乙酯、二苯甲酮、4-甲基二本甲酮、2-甲基-1-(4-甲硫基苯基)-2-吗啉基-1-丙酮、1-羟基环己基苯基甲酮、2-羟基-2-甲基-1-苯基-1-丙酮、2，2-二甲氧基-2-苯基苯乙酮(安息香双甲醚)、2-苄基-2-二甲基氨基-1-(4-吗啉苯基)丁酮、异丙基硫杂蒽酮、苯甲酰甲酸甲酯、4-二甲氨基苯甲酸乙酯中的一种或两种或多种构成；The photoinitiator is made of diphenyl (2,4,6-trimethylbenzoyl) phosphonium oxide, phenylbis (2,4,6-trimethylbenzoyl) phosphonium oxide, 2,4, Ethyl 6-trimethylbenzoylphenylphosphonate, benzophenone, 4-methyldimethanone, 2-methyl-1- (4-methylthiophenyl) -2-morpholine -1-Acetone, 1-Hydroxycyclohexylphenylketone, 2-Hydroxy-2-methyl-1-phenyl-1-propanone, 2,2-Dimethoxy-2-phenylacetophenone (Benzoin dimethyl ether), 2-benzyl-2-dimethylamino-1- (4-morpholinyl) butanone, isopropylthioanthrone, methyl benzoylformate, 4-di One or two or more of methylaminobenzoate;
所述偶氮类引发剂由2，2-偶氮二(2-脒基丙烷)二盐酸(V-50)、2，2-偶氮二(2-咪唑啉基丙烷)二盐酸(VA-044)、2，2-偶氮二异丁腈(AIBN)、2，2-偶氮二(2，4-二甲基戊腈)(ABVN)、偶氮二异丁酸二甲酯(AIBME)、2，2′-偶氮-二-(2-甲基丁腈)(AMBN)、2，2′-偶氮(2-甲基-N-(2-羟基乙基)丙酰胺)中的一种或两种或多种构成。The azo initiator is composed of 2,2-azobis (2-fluorenylpropane) dihydrochloride (V-50), 2,2-azobis (2-imidazolinylpropane) dihydrochloride (VA- 044), 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2,4-dimethylvaleronitrile) (ABVN), dimethyl azobisisobutyrate (AIBME ), 2,2′-azo-bis- (2-methylbutyronitrile) (AMBN), 2,2′-azo (2-methyl-N- (2-hydroxyethyl) propionamide) Of one or two or more.
所述的热分解引发剂由过氧化苯甲酰、叔丁基过氧化氢、过氧化苯甲酸叔丁酯、过硫酸铵、过硫酸钠、过硫酸钾、过氧化氢、2，2-偶氮二(2-脒基丙烷)二盐酸(V-50)、2，2-偶氮二(2-咪唑啉基丙烷)二盐酸(VA-044)、2，2-偶氮二异丁腈(AIBN)、2，2-偶氮二(2，4-二甲基戊腈)(ABVN)、偶氮二异丁酸二甲酯(AIBME)、2，2′-偶氮-二-(2-甲基丁腈)(AMBN)、2，2′-偶氮(2-甲基N-(2-羟基乙基)丙酰胺)中的一种或两种或多种构成。The thermal decomposition initiator comprises benzoyl peroxide, tert-butyl hydroperoxide, tert-butyl peroxybenzoate, ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, 2,2-coupling Azobis (2-fluorenylpropane) dihydrochloride (V-50), 2,2-azobis (2-imidazolinylpropane) dihydrochloride (VA-044), 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis (2,4-dimethylvaleronitrile) (ABVN), dimethyl azobisisobutyrate (AIBME), 2,2′-azo-bis- ( One or two or more of 2-methylbutyronitrile) (AMBN), 2,2'-azo (2-methylN- (2-hydroxyethyl) propionamide).
所述氧化还原反应是通过由氧化剂和还原剂组成的氧化还原引发剂来实现的，所述氧化还原引发剂的质量为所述四类单体质量的0.001～0.3％；The redox reaction is achieved by a redox initiator composed of an oxidizing agent and a reducing agent, and the mass of the redox initiator is 0.001 to 0.3% of the mass of the four types of monomers;
所述氧化剂由过硫酸铵、过硫酸钠、过硫酸钾、过氧化氢、叔丁基过氧化氢、过氧化苯甲酰、溴酸钠、溴酸钾中的一种或两种或多种构成；The oxidant is composed of one or two or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, sodium bromate, and potassium bromate;
所述还原剂由亚硫酸氢钠、亚硫酸钠、偏重亚硫酸钠、连二亚硫酸钠、硫酸亚铁、硫酸亚铁铵、 三乙胺、三乙醇胺、四甲基乙二胺中的一种或两种或多种构成；The reducing agent comprises one or two or more of sodium bisulfite, sodium sulfite, sodium bisulfite, sodium dithionite, ferrous sulfate, ferrous ammonium sulfate, triethylamine, triethanolamine, and tetramethylethylenediamine. Species composition
其中，所述氧化剂与所述还原剂的质量比为1∶3-3∶2。Wherein, the mass ratio of the oxidant to the reducing agent is 1: 3-3: 2.
实施例Examples
(1)均匀混合链转移剂、pH调节剂、螯合剂、水和/或有机溶剂及表面活性剂形成混合液；(1) uniformly mixing a chain transfer agent, a pH adjuster, a chelating agent, water and / or an organic solvent and a surfactant to form a mixed solution;
(2)将非离子单体A、非离子单体B、交联剂、改性单体、阴离子单体以及阳离子单体四类单体置于混合液中，通过惰性气体对其除氧；(2) Put non-ionic monomer A, non-ionic monomer B, cross-linking agent, modified monomer, anionic monomer and cationic monomer into the mixed liquid, and remove oxygen by inert gas;
(3)施加引发条件进行连锁聚合，在水溶液体系或者悬浮体系中获得水溶性聚丙烯酰胺聚合物，所获得的聚合物为液体状、或胶体状、或颗粒状，该聚合物经过干燥、筛分等加工手段成为颗粒状和/或粉状水溶性固体聚丙烯酰胺产品。(3) Initiating conditions for chain polymerization, and obtaining a water-soluble polyacrylamide polymer in an aqueous solution system or a suspension system. The obtained polymer is liquid, or colloidal, or granular, and the polymer is dried and sieved. Grading processing means granulated and / or powdered water-soluble solid polyacrylamide products.
具体为：按重量计，将去离子水、链转移剂、螯合剂、pH调节剂、非离子单体A、非离子单体B、交联剂、改性单体、阳离子单体、阴离子单体混合均匀，通氮气除氧30分钟，通氮气除氧30分钟，进行引发，反应结束后，胶体降温至80℃以下，进行造粒、干燥、筛分，获得水溶性两性固体聚丙烯酰胺产品。Specifically: by weight, deionized water, chain transfer agent, chelating agent, pH adjuster, non-ionic monomer A, non-ionic monomer B, cross-linking agent, modified monomer, cationic monomer, anionic monomer The mixture was uniformly mixed, deaerated with nitrogen for 30 minutes, deaerated with nitrogen for 30 minutes, and initiated. After the reaction was completed, the colloid was cooled to below 80 ° C, granulated, dried and sieved to obtain a water-soluble amphoteric solid polyacrylamide product .
实施例1-4、实施例5-8、实施例9-12、实施例13-16依次为经氧化还原引发、热引发、光引发、辐射引发方式制备水溶性两性固体聚丙烯酰胺，分别见表1、表2、表3、表4。Examples 1-4, 5-8, 9-12, and 13-16 are sequentially prepared by redox initiation, thermal initiation, photoinitiation, and radiation initiation, respectively. Table 1, Table 2, Table 3, Table 4.
实施例和对比例中，分子量检测方法如下：In the examples and comparative examples, the molecular weight detection methods are as follows:
用凝胶渗透色谱(GPC)进行重均分子量(M W)的测定，通过色谱图得到重均分子量，GPC测定装置及测试条件如下： The weight average molecular weight (M W ) was measured by gel permeation chromatography (GPC), and the weight average molecular weight was obtained from the chromatogram. The GPC measurement device and test conditions are as follows:
检测器：RID-10A(岛津公司)Detector: RID-10A (Shimadzu Corporation)
色谱柱：TSKgel G4000PWXLColumn: TSKgel G4000PWXL
流动相：磷酸缓冲液Mobile phase: phosphate buffer
柱流量：0.8mL/minColumn flow: 0.8mL / min
试样浓度：1.0g/LSample concentration: 1.0g / L
注入量：20μLInjection volume: 20 μL
表1Table 1
Figure PCTCN2018093383-appb-000038
Figure PCTCN2018093383-appb-000038
Figure PCTCN2018093383-appb-000039
Figure PCTCN2018093383-appb-000039
表2Table 2
Figure PCTCN2018093383-appb-000040
Figure PCTCN2018093383-appb-000040
Figure PCTCN2018093383-appb-000041
Figure PCTCN2018093383-appb-000041
表3table 3
Figure PCTCN2018093383-appb-000042
Figure PCTCN2018093383-appb-000042
Figure PCTCN2018093383-appb-000043
Figure PCTCN2018093383-appb-000043
Figure PCTCN2018093383-appb-000044
Figure PCTCN2018093383-appb-000044
表4Table 4
Figure PCTCN2018093383-appb-000045
Figure PCTCN2018093383-appb-000045
Figure PCTCN2018093383-appb-000046
Figure PCTCN2018093383-appb-000046
对比例Comparative example
根据现有技术，制备水溶液聚丙烯酰胺产品：According to the prior art, an aqueous polyacrylamide product is prepared:
(1)均匀混合链转移剂、pH调节剂、螯合剂、水形成混合液；(1) uniformly mix the chain transfer agent, pH adjuster, chelating agent, and water to form a mixed solution;
(2)将非离子单体A、非离子单体B、交联剂、改性单体、阴离子单体以及阳离子单体四类单体置于混合液中，通过惰性气体对其充分除氧；(2) Put non-ionic monomer A, non-ionic monomer B, cross-linking agent, modified monomer, anionic monomer and cationic monomer in the mixed liquid, and fully deoxidize them with inert gas. ;
具体为：按重量计，将去离子水、链转移剂、螯合剂、pH调节剂、非离子单体A、非离子单体B、交联剂、改性单体、阳离子单体、阴离子单体混合均匀，通氮气除氧30分钟，升温后加入引发剂，粘度达到后加入亚硫酸氢钠终止聚合，加入去离子水调节粘度和固含量，降温，出料，获得两性聚丙烯酰胺水溶液产品。对比例1-4实验见表5。Specifically: by weight, deionized water, chain transfer agent, chelating agent, pH adjuster, non-ionic monomer A, non-ionic monomer B, cross-linking agent, modified monomer, cationic monomer, anionic monomer The mixture is mixed uniformly, deaeration with nitrogen for 30 minutes, and the initiator is added after the temperature is raised. After the viscosity is reached, sodium bisulfite is added to terminate the polymerization. Deionized water is added to adjust the viscosity and solid content. The temperature is lowered and the material is obtained. . Comparative Examples 1-4 are shown in Table 5.
表5table 5
Figure PCTCN2018093383-appb-000047
Figure PCTCN2018093383-appb-000047
Figure PCTCN2018093383-appb-000048
Figure PCTCN2018093383-appb-000048
Figure PCTCN2018093383-appb-000049
Figure PCTCN2018093383-appb-000049
应用实施例Application Examples
采用纸厂回收箱板纸浆料进行测试，其叩解度为40°SR，在浆料中加入交联改性型固体两性聚丙烯酰胺的水溶液，搅拌10分钟，抄片。两性聚丙烯酰胺加入量为2.0～6kg/t(按商品固含量扣除水分后的用量)。经纸业成形器成形后再经标准纸业压榨机压榨，100～105℃烘干，然后检测纸张的耐破度、抗张、环压、耐折、内结合等强度性能，并测试滤水性能。表6给出了按上述方法所制备的交联改性型水溶性固体聚丙烯酰胺对纸张增强效果及其对滤水性能影响的应用数据。The test was carried out by using a recycled paperboard pulp from a paper mill. The degree of decomposition was 40 ° SR. An aqueous solution of a cross-linked modified amphoteric polyacrylamide was added to the pulp, stirred for 10 minutes, and copied. Amphoteric polyacrylamide is added in an amount of 2.0 to 6 kg / t (the amount after deducting moisture based on the solid content of the product). After being formed by a paper shaper, it is pressed by a standard paper press, dried at 100 to 105 ° C, and then tested for strength properties such as breakage resistance, tensile strength, ring pressure, folding resistance, internal bonding, etc., and tested for water filtration. performance. Table 6 shows the application data of the reinforcing effect of the cross-linked modified water-soluble solid polyacrylamide prepared by the above method on the paper and its effect on the water filtration performance.
表6添加交联改性型水溶性两性固体聚丙烯酰胺的纸张强度及滤水效果测试Table 6 Test of paper strength and water filtration effect of cross-linked modified water-soluble amphoteric solid polyacrylamide
Figure PCTCN2018093383-appb-000050
Figure PCTCN2018093383-appb-000050
Figure PCTCN2018093383-appb-000051
Figure PCTCN2018093383-appb-000051
实施例17-20是经本发明采用的聚合引发方式制备水溶性两性聚丙烯酰胺固体产品，见表7。Examples 17-20 are the preparation of a water-soluble amphoteric polyacrylamide solid product by the polymerization initiation method adopted in the present invention, as shown in Table 7.
表7Table 7
Figure PCTCN2018093383-appb-000052
Figure PCTCN2018093383-appb-000052
Figure PCTCN2018093383-appb-000053
Figure PCTCN2018093383-appb-000053
实施例21、22是经本发明采用的聚合引发方式制备水溶性两性聚丙烯酰胺固体产品。Examples 21 and 22 are prepared by using the polymerization initiation method of the present invention to prepare a water-soluble amphoteric polyacrylamide solid product.
实施例21Example 21
用环己烷350份、Span-80 20份做底料，加热使其溶解，混合均匀，冷凝回流，在搅拌状态下通惰性气体除氧，升温至70℃。然后将丙烯酰胺98份、甲基丙烯酸二甲胺基乙酯30份、N，N-亚甲基双丙烯酰胺0.15份、二甲基(二甲氨基)乙烯基硅烷4份、甲基丙烯酰氧乙基三甲基氯化铵14份、二甲基二烯丙基氯化铵6份、马来酸11份、烯丙基磺酸钠1.2份、EDTA-2Na 0.03份、稀盐酸2.5份、去离子水153份充分溶解作为滴加物料，将过硫酸铵0.2份和V50 0.1份经5份去离子水溶解后加至滴加物料中并搅拌均匀，然后将其缓慢滴加1.5小时至底料中，滴加结束后保温1h，然后升温至75℃反应1小时，加入液体石蜡0.5份，降至室温，快速过滤分离除去有机油相，用无水乙醇洗涤聚合物3次，然后真空恒温干燥6小时，得两性聚丙烯酰胺固体产品。通过GPC测试其分子量为65.4万。Use 350 parts of cyclohexane and 20 parts of Span-80 as the bottom material, heat it to dissolve, mix well, condense and reflux, pass in an inert gas to remove oxygen under stirring, and raise the temperature to 70 ° C. Then, 98 parts of acrylamide, 30 parts of dimethylaminoethyl methacrylate, 0.15 parts of N, N-methylenebisacrylamide, 4 parts of dimethyl (dimethylamino) vinylsilane, and methacryloyl 14 parts of oxyethyltrimethylammonium chloride, 6 parts of dimethyldiallylammonium chloride, 11 parts of maleic acid, 1.2 parts of sodium allylsulfonate, 0.03 parts of EDTA-2Na, 2.5 parts of dilute hydrochloric acid 153 parts of deionized water are fully dissolved as the dropping material, 0.2 parts of ammonium persulfate and 0.1 parts of V50 are dissolved in 5 parts of deionized water, added to the dropping material and stirred evenly, and then slowly added dropwise for 1.5 hours to In the bottom material, the temperature was maintained for 1 hour after the dropwise addition, and then the temperature was raised to 75 ° C. for 1 hour. After adding 0.5 parts of liquid paraffin, the temperature was lowered to room temperature. The organic oil phase was quickly separated by filtration, the polymer was washed 3 times with absolute ethanol, and then vacuumed. Dry at constant temperature for 6 hours to obtain an amphoteric polyacrylamide solid product. GPC test has a molecular weight of 654,000.
实施例22Example 22
用正庚烷350份、Span-40 22份做底料，加热使其溶解，混合均匀，冷凝回流，在搅拌状态下通惰 性气体除氧，升温至70℃。然后将丙烯酰胺73.5份、N，N-二甲基丙烯酰胺5份、甲基丙烯酸二甲胺基乙酯50份、季戊四醇三丙烯酸酯0.2份、烯丙基(二异丙基氨基)二甲基硅烷1.5份、丙烯酰氧乙基三甲基氯化铵14份、丙烯酸22份、次磷酸钠0.8份、EDTA-2Na 0.03份、稀硫酸2份、去离子水121份充分溶解作为滴加物料，将过硫酸铵0.2份经2份去离子水溶解后加至滴加物料中并搅拌均匀，然后将其缓慢滴加1.5小时至底料中，滴加结束后保温1小时，然后升温至75℃反应1小时，加入液体石蜡0.5份，降至室温，快速过滤分离除去有机油相，用无水乙醇洗涤聚合物3次，然后真空恒温干燥6小时，得两性聚丙烯酰胺固体产品。通过GPC测试其分子量为67.7万。Use 350 parts of n-heptane and 22 parts of Span-40 as the bottom material, heat to dissolve them, mix well, condense and reflux, and remove oxygen with an inert gas under stirring, and raise the temperature to 70 ° C. Then, 73.5 parts of acrylamide, 5 parts of N, N-dimethylacrylamide, 50 parts of dimethylaminoethyl methacrylate, 0.2 parts of pentaerythritol triacrylate, and allyl (diisopropylamino) dimethyl 1.5 parts of monosilane, 14 parts of acryloxyethyltrimethylammonium chloride, 22 parts of acrylic acid, 0.8 parts of sodium hypophosphite, 0.03 parts of EDTA-2Na, 2 parts of dilute sulfuric acid, and 121 parts of deionized water were fully dissolved as a dropwise addition For materials, dissolve 0.2 parts of ammonium persulfate in 2 parts of deionized water and add to the dropwise materials and stir well, then slowly add 1.5 hours to the bottom material. After the dropwise addition, keep it for 1 hour, then raise the temperature to The reaction was performed at 75 ° C for 1 hour, 0.5 parts of liquid paraffin was added, and the temperature was lowered to room temperature. The organic oil phase was quickly removed by filtration, the polymer was washed 3 times with anhydrous ethanol, and then dried under vacuum constant temperature for 6 hours to obtain an amphoteric polyacrylamide solid product. Its molecular weight was 677,000 by GPC.
上述实施例只为说明本发明的技术构思及特点，是一种优选的实施例，其目的在于熟悉此项技术的人士能够了解本发明的内容并据以实施，并不能以此限定本发明的保护范围。凡根据本发明的精神实质所作的等效变换或修饰，都应涵盖在本发明的。The above embodiment is only for explaining the technical concept and features of the present invention, and is a preferred embodiment. The purpose is that persons familiar with the technology can understand the content of the present invention and implement it accordingly. protected range. Any equivalent transformation or modification made according to the spirit and essence of the present invention should be covered by the present invention.
对于本领域技术人员而言，显然本发明专利不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明专利内。不应将权利要求中的任何附图标记视为限制所涉及的权利要求。It is obvious to a person skilled in the art that the patent of the present invention is not limited to the details of the above-mentioned exemplary embodiments, and the present invention can be implemented in other specific forms without departing from the spirit or basic features of the present invention. Therefore, the embodiments are to be regarded as exemplary and non-limiting in every respect, and the scope of the present invention is defined by the appended claims rather than the above description, and therefore is intended to fall within the claims. All changes within the meaning and scope of equivalent elements of the invention are included in the patent of the present invention. Any reference signs in the claims should not be construed as limiting the claims involved.

Claims (12)

  1. 一种交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述交联改性型水溶性固体聚丙烯酰胺至少由非离子单体A、非离子单体B、交联剂、改性单体、阳离子单体以及阴离子单体六类单体通过连锁聚合共聚而成，A cross-linked modified water-soluble solid polyacrylamide, characterized in that the cross-linked modified water-soluble solid polyacrylamide consists of at least a non-ionic monomer A, a non-ionic monomer B, a cross-linking agent, and a modified Sex monomer, cationic monomer and anionic monomer six kinds of monomers are made by chain polymerization copolymerization,
    所述的非离子单体A的结构通式I如下：The general formula I of the non-ionic monomer A is as follows:
    Figure PCTCN2018093383-appb-100001
    Figure PCTCN2018093383-appb-100001
    其中：R 1表示H或CH 3； Wherein: R 1 represents H or CH 3 ;
    R 2和R 3分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018093383-appb-100002
    R 2 and R 3 represent H, CH 3 , CH 2 CH 3 or
    Figure PCTCN2018093383-appb-100002
    所述的非离子单体B选自如下结构通式II-1、II-2、II-3所示的化合物中的一种或多种的组合：The non-ionic monomer B is selected from one or more combinations of the compounds represented by the following general formulae II-1, II-2, and II-3:
    Figure PCTCN2018093383-appb-100003
    Figure PCTCN2018093383-appb-100003
    其中：R 4表示H或CH 3； Wherein: R 4 represents H or CH 3 ;
    R 5表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
    Figure PCTCN2018093383-appb-100004
    R 5 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
    Figure PCTCN2018093383-appb-100004
    R 6和R 7表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018093383-appb-100005
    R 6 and R 7 represent H, CH 3 , CH 2 CH 3 or
    Figure PCTCN2018093383-appb-100005
    Figure PCTCN2018093383-appb-100006
    Figure PCTCN2018093383-appb-100006
    其中：R 8表示H或CH3； Wherein: R 8 represents H or CH 3;
    R 9、R 11和R 12分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018093383-appb-100007
    R 9 , R 11 and R 12 represent H, CH 3 , CH 2 CH 3 or
    Figure PCTCN2018093383-appb-100007
    R 10表示CH 2，CH 2CH 2、CH 2CH 2CH 2或
    Figure PCTCN2018093383-appb-100008
    R 10 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
    Figure PCTCN2018093383-appb-100008
    Figure PCTCN2018093383-appb-100009
    Figure PCTCN2018093383-appb-100009
    其中：R 13表示H或CH3； Wherein: R 13 represents H or CH3;
    R 14表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
    Figure PCTCN2018093383-appb-100010
    R 14 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
    Figure PCTCN2018093383-appb-100010
    R 15和R 16分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018093383-appb-100011
    R 15 and R 16 represent H, CH 3 , CH 2 CH 3 or
    Figure PCTCN2018093383-appb-100011
    所述的交联剂选自如下式III-1、III-2、III-3、III-4、III-5、III-6、或III-7所示的化合物：The cross-linking agent is selected from compounds represented by the following formulae III-1, III-2, III-3, III-4, III-5, III-6, or III-7:
    Figure PCTCN2018093383-appb-100012
    Figure PCTCN2018093383-appb-100012
    其中：R 17表示OH或CH 3； Wherein: R 17 represents OH or CH 3 ;
    R 18、R 19和R 20表示
    Figure PCTCN2018093383-appb-100013
    R 18 , R 19 and R 20 represent
    Figure PCTCN2018093383-appb-100013
    Figure PCTCN2018093383-appb-100014
    Figure PCTCN2018093383-appb-100014
    其中：R 21、R 22和R 23表示CH 2或CH 2CH 2； Wherein: R 21 , R 22 and R 23 represent CH 2 or CH 2 CH 2 ;
    Figure PCTCN2018093383-appb-100015
    Figure PCTCN2018093383-appb-100015
    其中：R 24、R 25、R 26、R 27表示CH 2、CH 2CH 2； Wherein: R 24 , R 25 , R 26 , and R 27 represent CH 2 and CH 2 CH 2 ;
    所述的改性单体包括改性单体A、改性单体B中的一种或两种；The modified monomer includes one or two of modified monomer A and modified monomer B;
    所述的改性单体A包含(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、丙烯腈、羟甲基丙烯酰胺、苯乙烯、乙烯基吡咯烷酮、4-乙烯基吡啶、(甲基)丙烯酸酯类单体中的一种或多种的组合；所述的(甲基)丙烯酸酯类单体的结构通式IV如下：The modified monomer A includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, acrylonitrile, hydroxymethacrylamide, styrene, vinylpyrrolidone, 4 A combination of one or more of vinylpyridine and (meth) acrylate monomers; the general formula IV of the (meth) acrylate monomers is as follows:
    Figure PCTCN2018093383-appb-100016
    Figure PCTCN2018093383-appb-100016
    其中：R 28表示H或CH 3； Wherein: R 28 represents H or CH 3 ;
    R 29表示H，CH 3，(CH 2) nCH 3，n≤6且为正整数； R 29 represents H, CH 3 , (CH 2 ) n CH 3 , n≤6 and a positive integer;
    所述的改性单体B为有机硅单体，包括3-(N-烯丙基氨基)丙基三甲氧基硅烷、二甲基(二甲胺基)乙烯基硅烷、烯丙基(二异丙基氨基)二甲基硅烷、乙烯基-三(2-甲氧基乙氧基)硅烷、烯丙基三甲氧基硅烷或如下结构通式(V)所示的化合物中的一种或多种形成的混合物，所述改性单体B的用量为所述改性单体质量的0.5wt.％～5wt.％；所述的结构通式(V)为：The modified monomer B is an organic silicon monomer, including 3- (N-allylamino) propyltrimethoxysilane, dimethyl (dimethylamino) vinylsilane, and allyl (di Isopropylamino) dimethylsilane, vinyl-tris (2-methoxyethoxy) silane, allyltrimethoxysilane or a compound represented by the following general formula (V) or A mixture of various forms, wherein the amount of the modified monomer B is 0.5 wt.% To 5 wt.% Of the mass of the modified monomer; and the structural formula (V) is:
    Figure PCTCN2018093383-appb-100017
    Figure PCTCN2018093383-appb-100017
    其中：R 30表示H或CH 3； Wherein: R 30 represents H or CH 3 ;
    R 31表示C 2～C 4的直链烷基； R 31 represents a C 2 to C 4 linear alkyl group;
    R 32、R 33、R 34表示C 1～C 4的烷基； R 32 , R 33 and R 34 represent C 1 to C 4 alkyl groups;
    所述的阳离子单体选自如下结构通式VI-1、VI-2、VI-3所示的化合物的季铵盐或酸中的一种或多种的组合：The cationic monomer is selected from one or more of quaternary ammonium salts or acids of the compounds represented by the following general formulas VI-1, VI-2, and VI-3:
    Figure PCTCN2018093383-appb-100018
    Figure PCTCN2018093383-appb-100018
    其中：R 35表示H或CH 3； Wherein: R 35 represents H or CH 3 ;
    R 36表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
    Figure PCTCN2018093383-appb-100019
    R 36 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
    Figure PCTCN2018093383-appb-100019
    R 37、R 38分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018093383-appb-100020
    R 37 and R 38 represent H, CH 3 , CH 2 CH 3 or
    Figure PCTCN2018093383-appb-100020
    Figure PCTCN2018093383-appb-100021
    Figure PCTCN2018093383-appb-100021
    其中：R 39表示H或CH 3； Wherein: R 39 represents H or CH 3 ;
    R 40、R 42和R 43分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018093383-appb-100022
    R 40 , R 42 and R 43 represent H, CH 3 , CH 2 CH 3 or
    Figure PCTCN2018093383-appb-100022
    R 41表示CH 2，CH 2CH 2、CH 2CH 2CH 2或
    Figure PCTCN2018093383-appb-100023
    R 41 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
    Figure PCTCN2018093383-appb-100023
    Figure PCTCN2018093383-appb-100024
    Figure PCTCN2018093383-appb-100024
    其中：R 44表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018093383-appb-100025
    Where: R 44 represents H, CH 3 , CH 2 CH 3 or
    Figure PCTCN2018093383-appb-100025
    所述的阴离子单体为如下结构通式VII-1、VII-2、VII-3、VII-4、VII-5或VII-6所示的化合物或其盐：The anionic monomer is a compound represented by the following general formula VII-1, VII-2, VII-3, VII-4, VII-5 or VII-6 or a salt thereof:
    Figure PCTCN2018093383-appb-100026
    Figure PCTCN2018093383-appb-100026
    其中：R4 7表示H，CH 3或CH 2COOH； Wherein: R4 7 represents H, CH 3 or CH 2 COOH;
    Figure PCTCN2018093383-appb-100027
    Figure PCTCN2018093383-appb-100027
    其中：R 48和R 49分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018093383-appb-100028
    Where: R 48 and R 49 represent H, CH 3 , CH 2 CH 3 or
    Figure PCTCN2018093383-appb-100028
    Figure PCTCN2018093383-appb-100029
    Figure PCTCN2018093383-appb-100029
    其中：R 50表示H或CH 3； Wherein: R 50 represents H or CH 3 ;
    Figure PCTCN2018093383-appb-100030
    Figure PCTCN2018093383-appb-100030
    其中：R 51表示H或CH 3； Wherein: R 51 represents H or CH 3 ;
    R 52表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018093383-appb-100031
    R 52 represents H, CH 3 , CH 2 CH 3 or
    Figure PCTCN2018093383-appb-100031
    R 53表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
    Figure PCTCN2018093383-appb-100032
    R 53 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
    Figure PCTCN2018093383-appb-100032
    Figure PCTCN2018093383-appb-100033
    Figure PCTCN2018093383-appb-100033
    其中：R 54表示H或CH 3； Wherein: R 54 represents H or CH 3 ;
    Figure PCTCN2018093383-appb-100034
    Figure PCTCN2018093383-appb-100034
    其中：R 55表示H或CH 3。 Wherein: R 55 represents H or CH 3 .
  2. 根据权利要求1所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述的固体聚丙烯酰胺的共聚物中六类单体质量比为：The cross-linked modified water-soluble solid polyacrylamide according to claim 1, wherein the mass ratio of six types of monomers in the copolymer of the solid polyacrylamide is:
    非离子单体A：40-90wt％；Non-ionic monomer A: 40-90wt%;
    非离子单体B：1-30wt％；Non-ionic monomer B: 1-30wt%;
    交联剂：0.005-0.2wt％；Crosslinking agent: 0.005-0.2wt%;
    改性单体：0.2-5wt％；Modified monomer: 0.2-5wt%;
    阳离子单体：1-30wt％；Cationic monomer: 1-30wt%;
    阴离子单体：0.3-30wt％。Anionic monomer: 0.3-30 wt%.
  3. 根据权利要求1所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述的固体聚丙烯酰胺为固体产品形式，其颗粒粒径小于5mm。The cross-linked modified water-soluble solid polyacrylamide according to claim 1, wherein the solid polyacrylamide is in the form of a solid product, and the particle diameter of the solid polyacrylamide is less than 5 mm.
  4. 根据权利要求3所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述的固体聚丙烯酰胺的颗粒粒径小于2mm。The crosslinked modified water-soluble solid polyacrylamide according to claim 3, wherein the particle diameter of the solid polyacrylamide is less than 2 mm.
  5. 根据权利要求1所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述的固体聚丙烯酰胺的重均分子量为10万-200万。The cross-linked modified water-soluble solid polyacrylamide according to claim 1, wherein the weight-average molecular weight of the solid polyacrylamide is from 100,000 to 2 million.
  6. 根据权利要求5所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述的固体聚丙烯酰胺的重均分子量为50-150万。The cross-linked modified water-soluble solid polyacrylamide according to claim 5, wherein the weight-average molecular weight of the solid polyacrylamide is from 500,000 to 1.5 million.
  7. 根据权利要求1所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述阳离子单体为所述结构通式VI-1，VI-2或VI-3所示的化合物季铵化后形成的季铵盐或该化合物与无机酸或有机酸反应后使用；和/或The cross-linked modified water-soluble solid polyacrylamide according to claim 1, wherein the cationic monomer is a compound quarter represented by the general formula VI-1, VI-2 or VI-3 Quaternary ammonium salt formed after ammonification or the compound is used after reacting with an inorganic or organic acid; and / or
    所述阴离子单体为所述结构通式VII-1，VII-2，VII-3，VII-4，VII-5或VII-6所示的化合物的碱金属盐、铵盐或碱土金属盐。The anionic monomer is an alkali metal salt, an ammonium salt, or an alkaline earth metal salt of the compound represented by the general formula VII-1, VII-2, VII-3, VII-4, VII-5, or VII-6.
  8. 根据权利要求1所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述连锁聚合为自由基聚合、阴离子聚合、阳离子聚合或配位聚合；和/或The cross-linked modified water-soluble solid polyacrylamide according to claim 1, wherein the chain polymerization is a radical polymerization, an anionic polymerization, a cationic polymerization, or a coordination polymerization; and / or
    所述连锁聚合选用光引发、热分解引发、氧化还原引发、辐射引发中的一种或多种。The chain polymerization is selected from one or more of photoinitiation, thermal decomposition initiation, redox initiation, and radiation initiation.
  9. 根据权利要求1所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述固体聚丙烯酰胺在水溶液体系或者悬浮聚合体系中获得。The crosslinked modified water-soluble solid polyacrylamide according to claim 1, wherein the solid polyacrylamide is obtained in an aqueous solution system or a suspension polymerization system.
  10. 根据权利要求9所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：所述水溶性固体聚丙烯酰胺为在体系中获得的液体、胶体或颗粒，并经过干燥、筛分后制得颗粒和/或粉状产品。The cross-linked modified water-soluble solid polyacrylamide according to claim 9, wherein the water-soluble solid polyacrylamide is a liquid, colloid, or granule obtained in the system, and is dried and sieved Granulated and / or powdered products are obtained.
  11. 根据权利要求1所述的交联改性型水溶性固体聚丙烯酰胺，其特征在于：在聚合前和/或聚合后加入表面活性剂、无机盐、尿素、二氧化硅、硅油、高沸点烃类化合物、天然高分子材料、人工合成的高分子材料、半天然半人工合成材料、矿物材料中的一种或多种；The cross-linked modified water-soluble solid polyacrylamide according to claim 1, characterized in that a surfactant, an inorganic salt, urea, silica, silicone oil, and a high-boiling hydrocarbon are added before and / or after the polymerization. One or more of compound, natural polymer material, synthetic polymer material, semi-natural semi-synthetic material, mineral material;
    所述的高沸点烃类混合物包括饱和烃、不饱和烃和芳香烃中的一种或多种；The high-boiling hydrocarbon mixture includes one or more of saturated hydrocarbons, unsaturated hydrocarbons, and aromatic hydrocarbons;
    所述的天然高分子材料选自纤维、淀粉、植物胶、动物胶或海藻胶；所述植物胶为阿拉伯胶、槐豆胶、黄芪胶、胍胶、田菁胶、大豆胶中的一种或多种；所述的动物胶为骨胶、明胶、干酪素、壳聚糖中的一种或多种；所述的海藻胶为藻蛋白酸钠、海藻酸钠、琼胶中的一种或多种；The natural polymer material is selected from the group consisting of fiber, starch, vegetable gum, animal gum, or seaweed gum; the vegetable gum is one of acacia gum, locust bean gum, astragalus gum, guanidine gum, tianjing gum, and soybean gum Or more; the animal glue is one or more of bone glue, gelatin, casein, and chitosan; the seaweed glue is one of sodium alginate, sodium alginate, or agar Multiple
    所述人工合成的高分子材料包括缩合类和聚合类高分子材料；其中，缩合类高分子材料选自聚胺树脂、氨基树脂和聚氨酯树脂中的一种或多种；聚合类高分子材料选自聚丙烯酰胺、聚丙烯酸、聚乙二醇、聚氧化乙烯、聚马来酸酐、聚季铵盐中的一种或多种；The artificially synthesized polymer materials include condensation-type and polymerization-type polymer materials; wherein, the condensation-type polymer materials are selected from one or more of polyamine resin, amino resin, and polyurethane resin; From one or more of polyacrylamide, polyacrylic acid, polyethylene glycol, polyethylene oxide, polymaleic anhydride, polyquaternium;
    所述的半天然半人工合成的高分子材料包括改性纤维、改性淀粉、改性纤维素和改性植物胶。The semi-natural semi-synthetic polymer material includes modified fiber, modified starch, modified cellulose and modified vegetable gum.
  12. 如权利要求1-11中任一项所述的交联改性型水溶性固体聚丙烯酰胺在天然纤维材料或者半合成纤维材料的增强和/或改性中的用途，所述的增强作用包括抗张、撕裂、耐破、环压、耐折、表面强度中的一种或多种。The use of the cross-linked modified water-soluble solid polyacrylamide according to any one of claims 1 to 11 in the reinforcement and / or modification of natural fiber materials or semi-synthetic fiber materials, wherein the reinforcing effect comprises One or more of tensile strength, tear resistance, burst resistance, ring pressure resistance, folding resistance, and surface strength.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1025691A (en) * 1997-03-24 1998-01-27 Mitsui Petrochem Ind Ltd Cationic polyacrylamide, paper strengthening agent for z-axis paper strength and interlaminar paper strength and drainage improver
EP1137679B1 (en) * 1998-11-05 2004-12-01 Basf Aktiengesellschaft Aqueous dispersions of water-soluble polymers of n-vinyl carboxylic acid amides, method for the production and use thereof
CN101033592A (en) * 2007-04-13 2007-09-12 陕西科技大学 Method of preparing cationic polyacrylamide paper making intensifier
CN101487207A (en) * 2009-02-16 2009-07-22 广州市星业科技发展有限公司 Production method of anti-interference paper intensifier
CN106866886A (en) * 2016-12-30 2017-06-20 浙江可思克高新材料股份有限公司 A kind of paper both sexes drying strengthening agent

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1025691A (en) * 1997-03-24 1998-01-27 Mitsui Petrochem Ind Ltd Cationic polyacrylamide, paper strengthening agent for z-axis paper strength and interlaminar paper strength and drainage improver
EP1137679B1 (en) * 1998-11-05 2004-12-01 Basf Aktiengesellschaft Aqueous dispersions of water-soluble polymers of n-vinyl carboxylic acid amides, method for the production and use thereof
CN101033592A (en) * 2007-04-13 2007-09-12 陕西科技大学 Method of preparing cationic polyacrylamide paper making intensifier
CN101487207A (en) * 2009-02-16 2009-07-22 广州市星业科技发展有限公司 Production method of anti-interference paper intensifier
CN106866886A (en) * 2016-12-30 2017-06-20 浙江可思克高新材料股份有限公司 A kind of paper both sexes drying strengthening agent

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