WO2018228040A1 - 一种水溶性固体聚丙烯酰胺及其用途 - Google Patents

一种水溶性固体聚丙烯酰胺及其用途 Download PDF

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WO2018228040A1
WO2018228040A1 PCT/CN2018/082914 CN2018082914W WO2018228040A1 WO 2018228040 A1 WO2018228040 A1 WO 2018228040A1 CN 2018082914 W CN2018082914 W CN 2018082914W WO 2018228040 A1 WO2018228040 A1 WO 2018228040A1
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water
polyacrylamide
soluble solid
solid polyacrylamide
monomer
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PCT/CN2018/082914
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French (fr)
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魏星光
史亚鹏
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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    • 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
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/04—Polymerisation in solution
    • C08F2/10—Aqueous solvent
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/54—Polymerisation initiated by wave energy or particle radiation by X-rays or electrons
    • 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
    • C08F4/00—Polymerisation catalysts
    • C08F4/40—Redox systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or 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 of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/24—Homopolymers or copolymers of amides or imides
    • C08L33/26—Homopolymers or copolymers of acrylamide or methacrylamide

Definitions

  • the invention belongs to the field of water-soluble polymer materials, and particularly relates to a novel water-soluble solid polyacrylamide and a use thereof.
  • Polyacrylamide as an excellent industrial additive can be divided into three categories according to product status: aqueous solution, emulsion type, solid type (or powder type). According to its chargeability, it can be divided into cationic polyacrylamide, anionic polyacrylamide, nonionic polyacrylamide and amphoteric polyacrylamide.
  • the amphoteric polyacrylamide has a range of applications due to the presence of both anionic and cationic groups in its molecule. The more extensive, compared with polyacrylamide containing a single anionic group or cationic group, not only has the comprehensive performance of both, but also has obvious anti-polyelectrolyte effect and wide pH adaptation range. These properties and characteristics are The wide application of amphoteric polyacrylamide provides strong support.
  • the aqueous solution amphoteric polyacrylamide products currently on the market are used for paper sheet reinforcement in papermaking, and the effect is obvious, especially in the application of lifting secondary reinforcement fiber reinforcement.
  • the aqueous amphoteric polyacrylamide product also has the following problems: First, the molecular weight is low, mostly in the range of 300,000-600,000. If a higher molecular weight product is required, the viscosity of the aqueous solution will increase with the increase of the molecular weight, affecting the product.
  • aqueous products have low solid content, the market is basically 15%-20%, more than 25% is very rare, if the content is increased, the viscosity will also Rise and affect the use.
  • the amphoteric polyacrylamide liquid product is prone to mildew and deterioration during storage due to the large amount of water. At the same time, the ester group in the molecular structure is easily hydrolyzed, resulting in a change in the molecular structure of the polymer and affecting the use effect.
  • the amphoteric polyacrylamide liquid product has high transportation cost and high packaging cost due to low solid content. 4.
  • the amphoteric polyacrylamide liquid product has a short shelf life. 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, at 15% and 20% effective content. Under the aqueous solution polymerization, the reaction temperature rises sharply in 20% (see: Temperature Control of AmPAM Paper Dry Strength Agent Production Process [J]. China Paper, 2014, 33(12): 19-23)).
  • Cisode No. CN107366182A discloses an acrylamide-based polymer which is a polymer of a polymerization component containing (meth)acrylamide, a quaternary ammonium monomer and a (meth)allylsulfonate, and It does not contain a nitrogen-containing crosslinkable monomer and a tertiary amine-based monomer.
  • the obtained polyacrylamide is an aqueous solution type, has a low effective substance content, high transportation cost, and is easily hydrolyzed.
  • the object of the present invention is to provide a novel water-soluble solid polyacrylamide product, which solves the problems of low molecular weight, low effective substance content, poor storage stability, short shelf life, and the like in the aqueous solution type amphoteric polyacrylamide product, and a higher molecular weight can be obtained.
  • the product has high effective content, low transportation cost, is not easy to be hydrolyzed, and is not easy to mold.
  • the invention also provides the use of the water-soluble solid polyacrylamide for the reinforcement and/or modification of natural or semi-synthetic fibrous materials.
  • the water-soluble solid polyacrylamide is at least composed of the nonionic monomer A, the nonionic monomer B, the cationic monomer and the anionic monomer.
  • the chain polymerization is copolymerized, and the structural formula of the four types of monomers is as follows:
  • the nonionic monomer A has the structural formula I as follows:
  • R 1 represents H or CH 3 ;
  • R 2 and R 3 represent H, CH 3 , CH 2 CH 3 or
  • the nonionic monomer B has a structural formula II comprising the formula II-1, II-2, II-3, and the specific structure is as follows:
  • 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 cationic monomer is a quaternary ammonium salt or an acid of the compound represented by the structural formula III, and the structural formula III comprises the formula III-1, III-2, III-3, and the specific structure is as follows:
  • R 17 represents H or CH 3 ;
  • R 18 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
  • R 19 and R 20 represent H, CH 3 , CH 2 CH 3 or
  • R 21 represents H or CH 3 ;
  • R 22 , R 24 and R 25 represent H, CH 3 , CH 2 CH 3 or
  • R 23 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
  • R 26 represents H, CH 3 , CH 2 CH 3 or
  • the compound represented by the above formula III-1, III-2, III-3 in the above formula III is subjected to methyl chloride, ethyl chloride, benzyl chloride, allyl chloride, dimethyl sulfate, sulfuric acid Ethyl ester or epichlorohydrin is used after forming a quaternary ammonium salt, and can also be used after reacting with an inorganic acid or an organic acid;
  • the anionic monomer is a compound represented by the structural formula IV or a salt thereof, and the structural formula IV comprises the formula IV-1, IV-2, IV-3, IV-4, IV-5, IV-6, specifically
  • the structure is as follows:
  • R 27 represents H, CH 3 or CH 2 COOH
  • R 28 and R 29 represent H, CH 3 , CH 2 CH 3 or
  • R 30 represents H or CH 3 ;
  • R 31 represents H or CH 3 ;
  • R 32 represents H, CH 3 , CH 2 CH 3 or
  • R 33 represents CH 2 , CH 2 CH 2 , CH 2 CH 2 CH 2 or
  • R 34 represents H or CH 3 ;
  • R 35 represents H or CH 3 ;
  • the sulfonic acid group, carboxyl group, and phosphonic acid group in the structural formula of the above formula IV include an alkali metal salt, an ammonium salt or an alkaline earth metal salt thereof.
  • the water-soluble solid polyacrylamide wherein the mass ratio of the four types of monomers in the copolymer of the solid polyacrylamide is:
  • Nonionic monomer A 40-90% by weight
  • Nonionic monomer B 1-30% by weight
  • Cationic monomer 1-30% by weight
  • Anionic monomer 0.3-30% by weight.
  • the water-soluble solid polyacrylamide which is in the form of a solid product having a particle size of less than 5 mm, preferably less than 2 mm.
  • the water-soluble solid polyacrylamide wherein the solid polyacrylamide has a molecular weight of 100,000 to 2,000,000 (weight average molecular weight), preferably 2 to 1.5 million.
  • weight average molecular weight 100,000 to 2,000,000 (weight average molecular weight), preferably 2 to 1.5 million.
  • the solid polyacrylamide has a molecular weight of 100,000 to 2,000,000 (weight average molecular weight), more preferably 3 to 1,000,000.
  • the water-soluble solid polyacrylamide wherein the cationic monomer is a quaternary ammonium salt formed by quaternization of a compound represented by the formula III-1, III-2 or III-3 or the compound and the inorganic acid or organic Used 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 of the formula IV-1, IV-2, IV-3, IV-4, IV-5 or IV-6.
  • the water-soluble solid polyacrylamide obtained by the chain polymerization of the nonionic monomer A, the nonionic monomer B, the cationic monomer and the anionic monomer obtained by the chain polymerization of the nonionic monomer A, the nonionic monomer B, the cationic monomer and the anionic monomer .
  • the water-soluble solid polyacrylamide, the chain polymerization is a radical polymerization, an anionic polymerization, a cationic polymerization or a coordination polymerization; and/or
  • the chain polymerization may take one or more of photoinitiation, thermal decomposition initiation, redox initiation, and radiation initiation.
  • the water-soluble solid polyacrylamide is characterized in that it can be obtained in an aqueous solution system or a suspension polymerization system.
  • the water-soluble solid polyacrylamide characterized in that the water-soluble solid polyacrylamide is a liquid, colloid or granule obtained in a system, and is dried and sieved to obtain a granulated product and/or a powdery product.
  • the water-soluble solid polyacrylamide characterized by adding a surfactant, an inorganic salt, a urea, a silica, a silicone oil, a high-boiling hydrocarbon compound, a natural polymer material, and a labor before and/or after the polymerization.
  • a surfactant an inorganic salt, a urea, a silica, a silicone oil, a high-boiling hydrocarbon compound, a natural polymer material, and a labor before and/or after the polymerization.
  • a synthetic polymer material characterized by adding a surfactant, an inorganic salt, a urea, a silica, a silicone oil, a high-boiling hydrocarbon compound, a natural polymer material, and a labor before and/or after the polymerization.
  • a synthetic polymer material characterized by adding a surfactant, an inorganic salt, a urea, a silica, a silicone oil, a
  • the high boiling hydrocarbon mixture includes one or more of a saturated hydrocarbon, an unsaturated hydrocarbon, and an aromatic hydrocarbon;
  • the natural polymer material is selected from the group consisting of fiber, starch, vegetable gum, animal glue or seaweed gum;
  • the vegetable gum is one of gum arabic, locust bean gum, tragacanth gum, tannin gum, phthalocyanine gum, and soybean gum.
  • the animal glue is one or more of bone glue, gelatin, casein, chitosan;
  • the seaweed gum is one of sodium alginate, sodium alginate, agar or Multiple
  • the synthetic polymer material comprises a condensation type and a polymer type polymer material; wherein the condensation type polymer material is selected from one or more of a polyamine resin, an amino resin and a polyurethane resin; One or more of polyacrylamide, polyacrylic acid, polyethylene glycol, polyethylene oxide, polymaleic anhydride, polyquaternium;
  • the semi-natural semi-synthetic synthetic polymer materials include modified fibers, modified starches, modified celluloses and modified vegetable gums.
  • the mineral material includes one or more of bentonite, modified bentonite, kaolin, zeolite, and diatomaceous earth.
  • the invention also employs the following technical solution: the use of the water-soluble solid polyacrylamide in the reinforcement and/or modification of natural fibrous materials or semi-synthetic fibrous materials in a papermaking system.
  • the water-soluble solid polyacrylamide is used as a papermaking reinforcing agent, as the molecular weight increases, the improvement of the drainage performance is promoted, and the strength is also improved, which is a polyacrylamide in the form of an aqueous solution.
  • the product is not achievable. It also helps to improve retention, water filtration performance, and reduce deposits, stickies, and more.
  • the reinforcing effects include one or more of tensile, tearing, bursting, ring pressing, folding resistance, surface strength and the like.
  • the solid form product of the higher molecular weight water-soluble amphoteric polyacrylamide can be obtained.
  • the solid product has the advantages of high effective content, low transportation cost, low hydrolysis, no mildew, and long shelf life.
  • the amphoteric polyacrylamide solid product of the invention has an effective substance of more than 85%, 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 invention conforms to the development direction of environmental protection, energy saving and low carbon, and is widely used in the fields of papermaking, water treatment, textile printing and dyeing, leather, petroleum, mining, building materials, daily chemical, medicine, agriculture, etc.
  • the application prospects, especially for natural fiber materials or semi-synthetic fiber materials have reinforcing and/or modifying effects.
  • a novel water-soluble solid amphoteric polyacrylamide was prepared according to the following procedure:
  • the grading processing means a granular and/or powdery water-soluble solid polyacrylamide product.
  • the chain transfer agent consists of a C1-C4 lower aliphatic 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 monomer.
  • 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 or sodium hydrogencarbonate. Or two or more compositions, the pH adjusting agent is used to control the pH in the entire 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 chelating agent has a mass of 0.001 to 0.1% by weight based on the total mass of the entire material.
  • the organic solvent is one or more of a linear alkane, 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 a preferred organic solvent.
  • the surfactant is a sorbitol fatty acid ester having an HLB of 2 to 12.
  • HLB 2 to 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 polymerization in which a monomer is initiated by an active center and rapidly chains up.
  • the chain polymerization requires an active center, which can be classified into a radical polymerization, a cationic polymerization, an anionic polymerization, and a coordination polymerization depending on the active center.
  • the linkage polymerization is a radical polymerization, an anionic polymerization, a cationic polymerization or a coordination polymerization; and/or
  • the chain polymerization may take one or more of photoinitiation, thermal decomposition initiation, redox initiation, and radiation initiation.
  • the photoreaction is achieved by one or more of a photoinitiator and/or an azo initiator; the photoinitiator has a mass of 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 monomer;
  • the photoinitiator is diphenyl (2,4,6-trimethylbenzoyl)phosphine oxide, phenylbis(2,4,6-trimethylbenzoyl)phosphine oxide, 2,4, Ethyl 6-trimethylbenzoylphenylphosphonate, benzophenone, 4-methyldimethyl ketone, 2-methyl-1-(4-methylthiophenyl)-2-morpholine 1-acetone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2,2-dimethoxy-2-phenyl phenyl Ketone (benzoin dimethyl ether), 2-benzyl-2-dimethylamino-1-(4-morpholinyl) butanone, isopropyl thioxanthone, methyl benzoylformate, 4- One or two or more of ethyl dimethylaminobenzoate;
  • the azo initiator is composed of 2,2-azobis(2-amidinopropane)dihydrochloride (V-50), 2,2-azobis(2-imidazolidinylpropane) 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) One or two or more of them.
  • the thermal decomposition initiator comprises benzoyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, 2,2-couple Nitros(2-amidinopropane) dihydrochloride (V-50), 2,2-azobis(2-imidazolidinylpropane) dihydrochloride (VA-044), 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis(2,4-dimethylvaleronitrile) (ABVN), dimethyl azobisisobutyrate (AIBME), 2,2'-azo-di-( One or two or more of 2-methylbutyronitrile) (AMBN) and 2,2'-azo (2-methyl-N-(2-hydroxyethyl)propionamide).
  • V-50 2,2-azobis(2-imidazolidinylpropane) dihydrochloride
  • AIBN 2,2-
  • the redox reaction is achieved by a redox initiator composed of an oxidizing agent and a reducing agent, the mass of the redox initiator being 0.001 to 0.3% by mass of the four types of monomers;
  • the oxidizing agent is composed of one or two or more of ammonium persulfate, sodium persulfate, potassium persulfate, hydrogen peroxide, t-butyl hydroperoxide, benzoyl peroxide, sodium bromate, potassium bromate;
  • the reducing agent is one or two or more of sodium hydrogen sulfite, sodium sulfite, sodium metabisulfite, sodium dithionite, ferrous sulfate, ammonium ferrous sulfate, triethylamine, triethanolamine, tetramethylethylenediamine.
  • the mass ratio of the oxidizing agent to the reducing agent is 1:3 to 3:2.
  • the grading processing means a granular and/or powdery water-soluble solid polyacrylamide product.
  • the deionized water, the chain transfer agent, the chelating agent, the pH adjuster, the nonionic monomer A, the nonionic monomer B, the cationic monomer, and the anionic monomer are uniformly mixed by weight, and the oxygen is removed by nitrogen. In a minute, oxygen was removed by nitrogen for 30 minutes, and after the reaction was completed, the colloid was cooled to 80 ° C or lower, granulated, dried, and sieved to obtain a water-soluble amphoteric solid polyacrylamide product.
  • Examples 1-4, Examples 5-8, Examples 9-12, and Examples 13-16 sequentially prepare water-soluble amphoteric solid polyacrylamides by redox initiation, thermal initiation, photoinitiation, and radiation initiation. Table 1, Table 2, Table 3, and Table 4.
  • the molecular weight detection method is as follows:
  • the weight average molecular weight (M W ) was measured by gel permeation chromatography (GPC), and the weight average molecular weight was obtained by a chromatogram.
  • GPC gel permeation chromatography
  • an aqueous polyacrylamide product is prepared:
  • the deionized water, the chain transfer agent, the chelating agent, the pH adjuster, the nonionic monomer A, the nonionic monomer B, the cationic monomer, and the anionic monomer are uniformly mixed by weight, and the oxygen is removed by nitrogen.
  • the initiator is added after the temperature is raised.
  • the viscosity is reached, the polymerization is terminated by adding sodium hydrogen sulfite, and the viscosity and solid content are adjusted by adding deionized water, and the temperature is lowered and discharged to obtain an amphoteric polyacrylamide aqueous solution product.
  • the experiments of Comparative Examples 1-4 are shown in Table 5.
  • the paper was used to carry out the test of the cardboard paper pulp, and the degree of enthalpy was 40°SR.
  • the solid amphoteric polyacrylamide aqueous solution was added to the slurry, stirred for 10 minutes, and the sheet was taken.
  • the amphoteric polyacrylamide is added in an amount of 2.0 to 6 kg/t (the amount of the solid content after deducting moisture).
  • After being formed by a paper former it is pressed by a standard paper press, dried at 100-105 ° C, and then tested for the burst strength, tensile strength, ring pressure, folding resistance, internal bonding and other strength properties of the paper, and testing the water filtration. performance.
  • Table 6 shows the application data of the water-soluble solid polyacrylamide prepared by the above method on the paper reinforcing effect and its influence on the drainage performance.
  • Examples 17-20 are water-soluble amphoteric polyacrylamide solid products prepared by the polymerization initiation method employed in the present invention, as shown in Table 7.
  • Examples 21 and 22 are preparations of a water-soluble amphoteric polyacrylamide solid product by the polymerization initiation method employed in the present invention.
  • cyclohexane 350 parts were used as a primer, heated to dissolve, uniformly mixed, condensed and refluxed, and deaerated by an inert gas under stirring to raise the temperature to 70 °C.
  • n-heptane and 22 parts of Span-40 were used as a base, heated to dissolve, uniformly mixed, condensed and refluxed, and deaerated by an inert gas under stirring to raise the temperature to 70 °C.
  • 73.5 parts of acrylamide, 5 parts of N,N-dimethylacrylamide, 50 parts of dimethylaminoethyl methacrylate, 14 parts of acryloyloxyethyltrimethylammonium chloride, 22 parts of acrylic acid, sodium formate 0.2 parts, 0.03 parts of EDTA-2Na, 2 parts of dilute sulfuric acid, 121 parts of deionized water are fully dissolved as a dropping material, 0.2 parts of ammonium persulfate is dissolved in 2 parts of deionized water, added to the dropping material and stirred uniformly.

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Abstract

一种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、阳离子单体以及阴离子单体四类单体连锁聚合共聚而成。所述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。

Description

一种水溶性固体聚丙烯酰胺及其用途
相关申请的交叉引用
本发明要求2017年6月16日提交的中国专利申请CN201710455621.2的优先权，其全部内容通过引用并入本发明中。
技术领域
本发明属于水溶性高分子材料领域，具体涉及一种新型水溶性固体聚丙烯酰胺及其用途。
背景技术
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。
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。
如徐烺，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))。
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。
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。
发明内容
本发明的目的是提供一种新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。
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、阳离子单体以及阴离子单体四类单体连锁聚合共聚而成，所述的四类单体的其结构通式如下：
所述的非离子单体A，其结构通式I如下：
Figure PCTCN2018082914-appb-000001
其中：R 1表示H或CH 3；
R 2和R 3表示H，CH 3，CH 2CH 3或
Figure PCTCN2018082914-appb-000002
所述的非离子单体B，其结构通式Ⅱ包含式Ⅱ-1、Ⅱ-2、Ⅱ-3，具体结构如下：
Figure PCTCN2018082914-appb-000003
其中：R 4表示H或CH 3；
R 5表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
Figure PCTCN2018082914-appb-000004
R 6和R 7表示H，CH 3，CH 2CH 3或
Figure PCTCN2018082914-appb-000005
Figure PCTCN2018082914-appb-000006
其中：
R 8表示H或CH 3；
R 9和R 11、R 12表示H，CH 3，CH 2CH 3或
Figure PCTCN2018082914-appb-000007
R 10表示CH 2，CH 2CH 2、CH 2CH 2CH 2或
Figure PCTCN2018082914-appb-000008
Figure PCTCN2018082914-appb-000009
其中：
R 13表示H或CH 3；
R 14表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
Figure PCTCN2018082914-appb-000010
R 15和R 16表示H，CH 3，CH 2CH 3或
Figure PCTCN2018082914-appb-000011
所述的阳离子单体为结构通式Ⅲ所示的化合物的季铵盐或酸，结构通式Ⅲ包含式Ⅲ-1、Ⅲ-2、Ⅲ-3，具体结构如下：
Figure PCTCN2018082914-appb-000012
其中：R 17表示H或CH 3；
R 18表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
Figure PCTCN2018082914-appb-000013
R 19、R 20表示H，CH 3，CH 2CH 3或
Figure PCTCN2018082914-appb-000014
Figure PCTCN2018082914-appb-000015
其中：
R 21表示H或CH 3；
R 22、R 24和R 25表示H，CH 3，CH 2CH 3或
Figure PCTCN2018082914-appb-000016
R 23表示CH 2，CH 2CH 2、CH 2CH 2CH 2或
Figure PCTCN2018082914-appb-000017
Figure PCTCN2018082914-appb-000018
其中：
R 26表示H，CH 3，CH 2CH 3或
Figure PCTCN2018082914-appb-000019
上述通式Ⅲ中所述得结构通式Ⅲ-1、Ⅲ-2、Ⅲ-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；
所述的阴离子单体为结构通式Ⅳ所示的化合物或其盐，结构通式Ⅳ包含式Ⅳ-1、Ⅳ-2、Ⅳ-3、Ⅳ-4、Ⅳ-5、Ⅳ-6，具体结构如下：
Figure PCTCN2018082914-appb-000020
其中：
R 27表示H，CH 3或CH 2COOH；
Figure PCTCN2018082914-appb-000021
其中：
R 28和R 29表示H，CH 3，CH 2CH 3或
Figure PCTCN2018082914-appb-000022
Figure PCTCN2018082914-appb-000023
其中：
R 30表示H或CH 3；
Figure PCTCN2018082914-appb-000024
其中：
R 31表示H或CH 3；
R 32表示H，CH 3，CH 2CH 3或
Figure PCTCN2018082914-appb-000025
R 33表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
Figure PCTCN2018082914-appb-000026
Figure PCTCN2018082914-appb-000027
其中：R 34表示H或CH 3；
Figure PCTCN2018082914-appb-000028
其中：R 35表示H或CH 3；
上述通式Ⅳ的结构式中的磺酸基、羧基、膦酸基包括它们的碱金属盐、铵盐或碱土金属盐。
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四类单体质量比为：
非离子单体A：40-90wt％；
非离子单体B：1-30wt％；
阳离子单体：1-30wt％；
阴离子单体：0.3-30wt％。
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。
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。
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。
所述的水溶性固体聚丙烯酰胺，所述阳离子单体为通式III-1，III-2或III-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
所述阴离子单体为通式IV-1，IV-2，IV-3，IV-4，IV-5或IV-6所示的化合物的碱金属盐、铵盐或碱土金属盐。
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、所述阳离子单体以及所述阴离子单体连锁聚合制得。
所述的水溶性固体聚丙烯酰胺，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
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。
所述的水溶性固体聚丙烯酰胺，其特征在于可以在水溶液体系或者悬浮聚合体系中获得。
所述的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。
所述的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；
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；
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；
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；
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。
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。
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。
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。
技术效果
本发明采用以上方案，相比现有技术具有如下优点：
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。
具体实施方式
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。
根据下述步骤制得新型水溶性固体两性聚丙烯酰胺：
(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；
(2)将非离子单体A、非离子单体B、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；
(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。
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％。
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。
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％。
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。
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。
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。
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
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。
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％；
所述光引发剂由二苯基(2,4,6-三甲基苯甲酰基)氧化膦、苯基双(2,4,6-三甲基苯甲酰基)氧化膦、2,4,6-三甲基苯甲酰基苯基膦酸乙酯、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-羟基环已基苯基甲酮、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；
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。
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。
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％；
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；
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；
其中，所述氧化剂与所述还原剂的质量比为1:3-3:2。
实施例
(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；
(2)将非离子单体A、非离子单体B、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；
(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。
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、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。
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。
实施例和对比例中，分子量检测方法如下：
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：
检测器：RID-10A(岛津公司)
色谱柱：TSKgel G4000PWXL
流动相：磷酸缓冲液
柱流量：0.8mL/min
试样浓度：1.0g/L
注入量：20μL
表1
Figure PCTCN2018082914-appb-000029
Figure PCTCN2018082914-appb-000030
表2
Figure PCTCN2018082914-appb-000031
Figure PCTCN2018082914-appb-000032
表3
Figure PCTCN2018082914-appb-000033
Figure PCTCN2018082914-appb-000034
表4
Figure PCTCN2018082914-appb-000035
Figure PCTCN2018082914-appb-000036
对比例
根据现有技术，制备水溶液聚丙烯酰胺产品：
(1)均匀混合链转移剂、pH调节剂、螯合剂、水形成混合液；
(2)将非离子单体A、非离子单体B、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；
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、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。
表5
Figure PCTCN2018082914-appb-000037
Figure PCTCN2018082914-appb-000038
应用实施例
采用纸厂回收箱板纸浆料进行测试，其叩解度为40°SR，在浆料中加入固体两性聚丙烯酰胺水溶液，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。
表6 添加水溶性两性固体聚丙烯酰胺的纸张强度及滤水效果测试
Figure PCTCN2018082914-appb-000039
Figure PCTCN2018082914-appb-000040
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。
表7
Figure PCTCN2018082914-appb-000041
Figure PCTCN2018082914-appb-000042
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。
实施例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、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、异丙醇1 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63.3万。
实施例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、丙烯酰氧乙基三甲基氯化铵14份、丙烯酸22份、甲酸钠0.2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72.1万。
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。
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。

Claims (12)

  1. 一种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至少由非离子单体A、非离子单体B、阳离子单体以及阴离子单体四类单体通过连锁聚合共聚而成，
    所述的非离子单体A的结构通式I如下：
    Figure PCTCN2018082914-appb-100001
    其中：R 1表示H或CH 3；
    R 2和R 3分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018082914-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的化合物中的一种或多种的组合：
    Figure PCTCN2018082914-appb-100003
    其中：R 4表示H或CH 3；
    R 5表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
    Figure PCTCN2018082914-appb-100004
    R 6和R 7表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018082914-appb-100005
    Figure PCTCN2018082914-appb-100006
    其中：R 8表示H或CH 3；
    R 9、R 11和R 12分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018082914-appb-100007
    R 10表示CH 2，CH 2CH 2、CH 2CH 2CH 2或
    Figure PCTCN2018082914-appb-100008
    Figure PCTCN2018082914-appb-100009
    其中：R 13表示H或CH 3；
    R 14表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
    Figure PCTCN2018082914-appb-100010
    R 15和R 16分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018082914-appb-100011
    所述的阳离子单体选自如下结构通式Ⅲ-1、Ⅲ-2、Ⅲ-3所示的化合物的季铵盐或酸中的一种或多种的组合：
    Figure PCTCN2018082914-appb-100012
    其中：R 17表示H或CH 3；
    R 18表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
    Figure PCTCN2018082914-appb-100013
    R 19、R 20分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018082914-appb-100014
    Figure PCTCN2018082914-appb-100015
    其中：R 21表示H或CH 3；
    R 22、R 24和R 25分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018082914-appb-100016
    R 23表示CH 2，CH 2CH 2、CH 2CH 2CH 2或
    Figure PCTCN2018082914-appb-100017
    Figure PCTCN2018082914-appb-100018
    其中：R 26表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018082914-appb-100019
    所述的阴离子单体为如下结构通式Ⅳ-1、Ⅳ-2、Ⅳ-3、Ⅳ-4、Ⅳ-5或Ⅳ-6所示的化合物或其盐：
    Figure PCTCN2018082914-appb-100020
    其中：R 27表示H，CH 3或CH 2COOH；
    Figure PCTCN2018082914-appb-100021
    其中：R 28和R 29分别表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018082914-appb-100022
    Figure PCTCN2018082914-appb-100023
    其中：R 30表示H或CH 3；
    Figure PCTCN2018082914-appb-100024
    其中：R 31表示H或CH 3；
    R 32表示H，CH 3，CH 2CH 3或
    Figure PCTCN2018082914-appb-100025
    R 33表示CH 2，CH 2CH 2，CH 2CH 2CH 2或
    Figure PCTCN2018082914-appb-100026
    Figure PCTCN2018082914-appb-100027
    其中：R 34表示H或CH 3；
    Figure PCTCN2018082914-appb-100028
    其中：R 35表示H或CH 3。
  2. 根据权利要求1所述的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四类单体质量比为：
    非离子单体A：40-90wt％；
    非离子单体B：1-30wt％；
    阳离子单体：1-30wt％；
    阴离子单体：0.3-30wt％。
  3. 根据权利要求1所述的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。
  4. 根据权利要求3所述的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。
  5. 根据权利要求1所述的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。
  6. 根据权利要求5所述的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。
  7. 根据权利要求1所述的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III-1，III-2或III-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，所述阴离子单体为所述结构通式IV-1，IV-2，IV-3，IV-4，IV-5或IV-6所示的化合物的碱金属盐、铵盐或碱土金属盐。
  8. 根据权利要求1所述的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
    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。
  9. 根据权利要求1所述的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。
  10. 根据权利要求9所获得的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。
  11. 根据权利要求1所述的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；
    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；
    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；
    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；
    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。
  12. 如权利要求1-11中任一项所述的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。
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