CN105131162A - Water-soluble low-crosslinking polymaleic anhydride-diisobutylene copolymer salt dispersant and preparation method thereof - Google Patents
Water-soluble low-crosslinking polymaleic anhydride-diisobutylene copolymer salt dispersant and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a technological method for preparing water-soluble low-crosslinking polymaleic anhydride-diisobutylene copolymer salt dispersant. According to the dispersant, a third monomer is added as a cross-linking agent for achieving light crosslinking of a system in the polymerization process, and the usability of the polymerization system is upgraded. The technology that saponification is conducted immediately after the polymerization, organic solvent is removed through the oil-water separation and membrane separation technologies, the defects that in a traditional technology, namely polymerization, distillation and saponification, energy is consumed and the efficiency is low are avoided, the preparation process is simplified, and the preparation efficiency is remarkably improved. The dispersant obtained through the method has the advantages that the water solubility and light crosslinking characteristic are achieved simultaneously, and the crosslinking degree reaches 16.8%-22.7%; the operating temperature is raised, and the glass-transition temperature of polymer reaches 78.5 DEG C-82.5 DEG C; the dispersion force of the system is 95-130 mg/MnO<2> per 100 ml of sample solutions, wherein the concentration of the sample solutions is 0.025%. Therefore, the water-soluble low-crosslinking polymaleic anhydride-diisobutylene copolymer salt dispersant has a good application prospect in such fields as solution polymerized styrene-butadiene rubber, coating dispersion technology and leather tanning agent dispersion technology.
Description
Technical field
The present invention relates to a kind of water-soluble low cross-linking co-poly carboxylic acid dipersant and preparation method thereof, this dispersion agent is mainly used in solution polymerized butadiene styrene rubber dispersion technology field, also can be used for the fields such as coating dispersion, leather retanning agent dispersion technology.
Background technology
Dispersion agent (Dispersant) is a kind of interfacial agent simultaneously in molecule with lipophilicity and wetting ability two kinds of opposite nature.Can homogeneous dispersion those be difficult to be dissolved in the inorganic of liquid, the solid particulate of pigment dyestuff, also can prevent sedimentation and the cohesion of solid particulate simultaneously, forms stable medicament needed for suspension.Tradition dispersion agent has certain dissemination to solid particulate in dispersion medium, but because they are insecure in the absorption of particle surface, easily causes dispersed particle assemble again or precipitate from desorption particle surface.Due to the limitation of traditional dispersion agent, the macromolecule dispersing agent exploitation of dispersing property excellence just becomes the inexorable trend of development.
The stable mechanism of macromolecule dispersing agent both can increase particle surface electrostatic repulsion, can also strengthen sterically hindered effect, thus reach more stable dispersion effect by strengthening the thickness of Adsorbed polymer layers.With inorganic dispersant or organic dispersing agent as compared with alkylbenzene sulfonate, alkylphenol polyoxyethylene, naphthalenesulfonate formaldehyde condensation compound, sulfonated lignin etc., although structural similitude, performance has fairly obvious superiority.The copolyreaction of alpha-olefin and maleic anhydride and copolymer dispersant are a kind of dispersion agents of environment-friendly type, are widely used in coal water slurry, building concrete, the industries such as fuel, and it has a extensive future, and will more and more receive the concern of people.As the copolymerization systems such as phenylethylene-maleic anhydride, dicyclopentadiene-maleic anhydride, vinyl acetate-maleic anhydride are all widely studied.Wherein common, be also simultaneously that to be studied system the most deep be styrene-maleic anhydride copolymer.But this multipolymer has the higher shortcoming of second-order transition temperature.Diisobutylene-maleic anhydride system overcomes the shortcoming of polystyrene systems, and the copolymerization system of diisobutylene carbon chain length, composition has the advantages such as many, the sterically hindered effects of activated adsorption point are stable, has good application prospect.
Report about diisobutylene-maleic anhydride system preparation and modification is few.Document [petrochemical complex, 1992,21 (11), 743-746] describe a kind of syntheses and properties method of Diisobutylene-copolymer-maleic anhydride, polymers soln adopts industrial spirit precipitation or adopts steam distillation to be steamed by solvent, and technique is more complicated, complex operation, cost is higher, and adopts industrial spirit, and operation has danger.Document [Chinese leather, 2010,39 (11), 6-10] describe the preparation of a kind of diisobutylene-maleic anhydride amphipathic copolymer sodium salt retanning agent, carry out saponification again after adopting vacuum distillation method removing organic solvent, removal of solvents is incomplete, can introduce impurity after saponification.Document [Chinese patent, CN102532382A] and document [U.S.Patent2,725,367] come at maleic anhydride and diisobutylene to add three components in the system of copolymerization, the former introduces vinylformic acid, and the latter introduces Vinylstyrene, and use properties is improved, but still adopting underpressure distillation means removing organic solvent, contaminant problem still cannot solve.
In sum, polymerization and saponification separate and carry out by maleic anhydride-diisobutylene copolymer salt technique prepared by existing method, comparatively complicated, and adopt distillating method removing organic solvent, consume energy and be difficult to remove completely, cause the increase of this multipolymer cost, and the copolymer salt obtained being water-soluble linear polymer, second-order transition temperature is lower, also limit it at the temperature that solution polymerized butadiene styrene rubber etc. the is higher application of (being greater than 120 DEG C).The present invention, in order to overcome above shortcoming, carries out saponification reaction after monomer polymerization at once, and after forming cooling, a solvent part adopts oily water separation mode to be separated, and a part adopts membrane filtration pattern to be separated, and the method is compared with the method for document, and technique is simple, is separated completely; In addition, introduce Third monomer crosslinkable monomers in the course of the polymerization process, copolymer systems is occurred lightly crosslinked, do not changing the resistance toheat water miscible basis being improved copolymer systems, improve the use range of copolymer systems.
Summary of the invention
The object of the invention is to provide a kind of water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof.
Technical scheme of the present invention is: add in reaction vessel by the organic solvent of metering, maleic anhydride, diisobutylene, Third monomer, stir, be warming up to assigned temperature, logical nitrogen flooding is except oxygen, add initiator solution with certain speed, in certain hour, complete polyreaction.In polymerization system, add a small amount of catalyzer carry out crosslinking reaction.In polymeric system, slowly alkaline solution is added afterwards in violent stirring process, cool after saponification certain hour, isolate upper strata organic solvent, be separated after lower floor's saponification resultant suction filtered through kieselguhr removing solid impurity by membrane module, isolate remaining organic solvent, a kind of water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent after membrane sepn, can be prepared.
Easily there is alternating copolymerization in the maleic anhydride described in above-mentioned steps and diisobutylene, and not easily autohemagglutination.Diisobutylene substituent pushes away electro, is unfavorable for radical polymerization, and maleic anhydride is zero due to substituent space steric effect and moment of dipole, is also difficult to homopolymerization with this understanding.Therefore in two monomers, any component is excessive all can not carry out fine copolymerization.According to cross propagation or complexing Growth Mechanism, two kinds of monomers are comparatively large due to polarity spectrum, only have when maleic anhydride is 1: 1 with the mol ratio of diisobutylene, just can make two monomer reactions completely, make monomer conversion the highest.
Organic solvent described in above-mentioned steps need not be particularly limited to, and the organic solvents such as benzene,toluene,xylene, ethyl acetate, dioxan are used alone with used in combination, and the performance impact of change to copolymer systems of its ratio is not obvious.Solvent load is can dissolve maleic anhydride for measurement standard, the weight ratio of solvent and maleic anhydride is 1: (0.8 ~ 1.1), solvent ratios is too high, and monomer concentration declines, and can reduce polymerization efficiency, solvent ratios is too low, dissolution time extends, and monomer concentration is too high, also can affect polymerization system molecular weight, experiment finds that weight ratio is 1: time (0.8 ~ 1.1), effect is better.
Third monomer described in above-mentioned steps is Crosslinkable acrylic monomer, is preferably one or both in N hydroxymethyl acrylamide, diacetone-acryloamide(DAA), hydroxyethyl methylacrylate, glycidyl methacrylate, acrylate, pentaerythritol.The mol ratio of Third monomer and maleic anhydride is (0.05-0.1): 1.Third monomer too high levels can cause monomer crosslinkedly spends height, the water-soluble decline of polymeric system, even may precipitating generation; Otherwise then degree of crosslinking is inadequate, and resistance toheat does not reach requirement, experiment finds that with maleic anhydride mol ratio be (0.05-0.1): when 1, effect is better.
Initiator described in above-mentioned steps need not be particularly limited to, benzoyl peroxide, dodecanoyl, hydrogen peroxide, the material that isopropyl benzene hydroperoxide etc. are similar, be used alone with used in combination, the performance impact of change to copolymer systems of its ratio is not obvious, and initiator amount is the 0.005-0.008 of maleic anhydride quality.
Polymeric reaction temperature described in above-mentioned steps, selects at 80 DEG C ~ 90 DEG C.Along with the rising of temperature, monomer conversion increases, and the intrinsic viscosity of product declines.This is because the raising of temperature, can accelerate the decomposition of initiator on the one hand, active centre number in system is increased, and polymerization velocity is accelerated; On the other hand, temperature rising can accelerate end stopping of chain, and molecular weight of product is declined.Experiment finds that polymerization temperature controls to be advisable at 80 DEG C ~ 90 DEG C.
Polymerization reaction time described in above-mentioned steps, selected at 4 ~ 8 hours.Reaction times is longer, and monomer conversion is higher, and the change of the intrinsic viscosity of product is little.This meets general radical polymerization rule.Illustrate that the reaction times is longer, monomer reaction more complete, the chain tra nsfer of polymerization later stage undirected monomer or solvent.Experiment finds that reaction is be advisable for 4 ~ 8 hours.
Catalyzer described in above-mentioned steps need not be particularly limited to, and is generally volatile water-soluble amine, as methylamine, and dimethylamine, triethylamine, ethamine, diethylamine, Isopropylamine, quadrol, urotropine etc.Catalyst levels is 5% ~ 7% of Third monomer quality.
The kind of the alkaline solution of saponification described in above-mentioned steps is sodium hydroxide, potassium hydroxide, ammoniacal liquor etc., its concentration is 25%-30%, the mol ratio of alkali and maleic anhydride is 2: 1, alkaline solution plays and participates in reacting and playing katalysis in saponification process, ratio is herein unsuitable too high, otherwise reaction can be caused too fast, and system bubble is serious, cause system pressure to increase, and solution can be caused to turn to be yellow; Too low, speed of response can be caused slow.When experiment finds that alkali concn is 25%-30%, effect is better.
Saponification reaction temperature described in above-mentioned steps, selects at 95 DEG C ~ 99 DEG C.If temperature is higher than 100 DEG C, need to adopt oil bath heating; On the other hand, if temperature is too low, then saponification speed is slow.Experiment finds that saponification temperature is advisable at 95 DEG C ~ 99 DEG C.
The saponification reaction time described in above-mentioned steps, select at 1 ~ 1.5 hour.Saponification can terminate after certain reaction process, and the reaction times is long, can not improve transformation efficiency.Experiment finds that reaction is be advisable for 1 ~ 1.5 hour.
Oil-water separation method described in above-mentioned steps, after saponification reaction completes stop stir, reaction system leave standstill 2 ~ 2.5 hours, from reactor bottom release polymerization system, when in the system observing releasing floating have oil bloom after stop blanking.
Membrane separating method described in above-mentioned steps is the polymerization system of will release from reactor bottom, first by suction filtered through kieselguhr device removing solid matter, then is separated further by ceramic membrane device, and the membranous type number selected is JWCM07*30.
The method of the water-soluble low cross-linking polymaleic anhydride prepared-diisobutylene copolymer salt dispersion agent science characterizes, such as, products therefrom outward appearance is weak yellow liquid, the solid content measuring system by flash baking method is 21.5%-26.5%, measuring system pH with pH meter is 10.5 ~ 11.2, uses MnO
2dispersion method characterizes the dispersing property of dispersion agent, and result shows that the dispersion force of system is 95 ~ 130 [mgMnO
2/ 100ml sample solution (0.025%)], good dispersion property.Determined the degree of crosslinking of product by extraction by propanone, result shows that the degree of crosslinking of system is 16.8% ~ 22.7%, the slight crosslinked raising being conducive to use temperature, and the second-order transition temperature measuring polymerization system by DSC, reaches 78.5 DEG C ~ 82.5 DEG C.
In sum, technique effect of the present invention is obvious.The present invention introduces Third monomer, by lightly crosslinked raising polymerization system heat resisting temperature, solves the low grade of original polymaleic anhydride-diisobutylene polymerization system use temperature not enough, can be applicable to the solution polymerized butadiene styrene rubber field of dispersions that temperature is higher; In addition, the present invention, by polymerization process and saponification process being combined, simplifies the technological process of original polymerization-distillation-saponification, reduces production cost, make it to be easier to industrialization.The more important thing is, the present invention utilizes oily water separation and membrane separation technique Separation of Organic, avoid the still-process of power consumption, simplify preparation technology, improve product purity, preparation process is green, and preparation efficiency significantly improves simultaneously, has good application prospect at FIELD OF THE INVENTIONThe such as solution polymerized butadiene styrene rubber dispersion technology, coating dispersion, leather retanning agent dispersion technologies.
Accompanying drawing explanation
Fig. 1 is preparation technology's schema of the present invention.The explanation of Main Reference Numerals: 1, violent stirring process; 2, slowly alkaline solution is added, saponification reaction; 3, be generally separated; 4, suction filtered through kieselguhr is separated; 5, membrane module is separated.
Embodiment
In order to better the present invention is described, attached embodiment is as follows.It is emphasized that embodiment and do not mean that scope of the present invention is limited in the condition that embodiment describes, the object of embodiment sets forth content of the present invention and feasibility thereof further.
Embodiment 1:
(1) synthesis of multipolymer: by reactant 33.6g diisobutylene, 29.4g maleic anhydride, 1.52gN-n-methylolacrylamide, the solvent benzol of 32g and 0.15gBPO join is furnished with thermometer, in the there-necked flask of electric mixer and prolong.From a mouth of plug in thermometer, pass into 2min nitrogen, make shielding gas.With water-bath heating, polymerization temperature is made to control at 80 DEG C, polyreaction 8 hours.In system, add 0.09g quadrol after polymerization terminates and carry out crosslinking reaction.
(2) saponification of multipolymer: add 24g sodium hydroxide 70g deionized water in polymerization system.Airtight stirring heating 1.5 hours in the water-bath of constant temperature 95 DEG C.
(3) separation of multipolymer: mixed system the most obtained left standstill after 2.5 hours, lower floor's solution is obtained by oily water separation, lower floor's solution obtains through suction filtered through kieselguhr the translucent solution that there are a small amount of oil bloom on flaxen upper strata, this solution obtains light yellow transparent solution through membrane sepn again, obtains water-soluble low cross-linking polymaleic anhydride-diisobutylene multipolymer sodium salt dispersion agent product.(pH value=10.8, dispersion force is 103 [mgMnO for weak yellow liquid, solid content 23%
2/ 100ml sample solution (0.025%)], degree of crosslinking=16.5%, second-order transition temperature 78.7 DEG C)
Embodiment 2:
(1) synthesis of multipolymer: by reactant 33.6g diisobutylene, 29.4g maleic anhydride, 5.3g pentaerythritol triacrylate, the solvent ethyl acetate of 30g and 0.2gBPO join is furnished with thermometer, in the there-necked flask of electric mixer and prolong.From a mouth of plug in thermometer, pass into 2min nitrogen, make shielding gas.With water-bath heating, polymerization temperature is made to control at 90 DEG C, polyreaction 4 hours.In system, 0.09g methylamine is added and 0.18g diethylamine carries out crosslinking reaction after polymerization terminates.
(2) saponification of multipolymer: add 75g strong aqua (mass concentration 28%) in polymerization system.Airtight stirring heating 1 hour in the water-bath of constant temperature 95 DEG C.
(3) separation of multipolymer: mixed system the most obtained left standstill after 2 hours, lower floor's solution is obtained by oily water separation, lower floor's solution obtains through suction filtered through kieselguhr the translucent solution that there are a small amount of oil bloom on flaxen upper strata, this solution obtains light yellow transparent solution through membrane sepn again, obtains water-soluble low cross-linking polymaleic anhydride-diisobutylene multipolymer sodium salt dispersion agent product.(weak yellow liquid, solid content 26.1%, pH value=10.6, dispersion force is 110 [mgMnO2/100ml sample solution (0.025%)], degree of crosslinking=19.3%, second-order transition temperature 79.8 DEG C)
Embodiment 3:
(1) synthesis of multipolymer: by reactant 33.6g diisobutylene, 29.4g maleic anhydride, the mixed solvent of 2.7g glycidyl methacrylate, 18g benzene and 18g dimethylbenzene, 0.18g hydrogen peroxide joins is furnished with thermometer, in the there-necked flask of electric mixer and prolong.From a mouth of plug in thermometer, pass into 2min nitrogen, make shielding gas.With water-bath heating, polymerization temperature is made to control at 80 DEG C, polyreaction 6 hours.In system, 0.08g ethamine is added and 0.08g triethylamine carries out crosslinking reaction after polymerization terminates.
(2) saponification of multipolymer: add 24g sodium hydroxide 65g deionized water in polymerization system.Airtight stirring heating 1 hour in the water-bath of constant temperature 99 DEG C.
(3) separation of multipolymer: mixed system the most obtained left standstill after 2 hours, lower floor's solution is obtained by oily water separation, lower floor's solution obtains through suction filtered through kieselguhr the translucent solution that there are a small amount of oil bloom on flaxen upper strata, this solution obtains light yellow transparent solution through membrane sepn again, obtains water-soluble low cross-linking polymaleic anhydride-diisobutylene multipolymer sodium salt dispersion agent product.(weak yellow liquid, solid content 25.8%, pH value=10.9, dispersion force is 108 [mgMnO2/100ml sample solution (0.025%)], degree of crosslinking=18.2%, second-order transition temperature 79.2 DEG C)
Embodiment 4:
(1) synthesis of multipolymer: by reactant 33.6g diisobutylene, 29.4g maleic anhydride, 1.4gN-n-methylolacrylamide and 1.4g hydroxyethyl methylacrylate, the solvent toluene of 27g, 0.23g isopropyl benzene hydroperoxide joins is furnished with thermometer, in the there-necked flask of electric mixer and prolong.From a mouth of plug in thermometer, pass into 2min nitrogen, make shielding gas.With water-bath heating, polymerization temperature is made to control at 80 DEG C, polyreaction 4 hours.In system, add 0.14g diethylamine after polymerization terminates and carry out crosslinking reaction.
(2) saponification of multipolymer: add 33.6 potassium hydroxide 80g deionized waters in polymerization system.Airtight stirring heating 1.2 hours in the water-bath of constant temperature 97 DEG C.
(3) separation of multipolymer: mixed system the most obtained left standstill after 2 hours, lower floor's solution is obtained by oily water separation, lower floor's solution obtains through suction filtered through kieselguhr the translucent solution that there are a small amount of oil bloom on flaxen upper strata, this solution obtains light yellow transparent solution through membrane sepn again, obtains water-soluble low cross-linking polymaleic anhydride-diisobutylene multipolymer sodium salt dispersion agent product.(weak yellow liquid, solid content 24.3%, pH value=11.2, dispersion force is 119 [mgMnO2/100ml sample solution (0.025%)], degree of crosslinking=21.1%, second-order transition temperature 81.3 DEG C)
Embodiment 5:
(1) synthesis of multipolymer: by reactant 33.6g diisobutylene, 29.4g maleic anhydride, 3.5g diacetone-acryloamide(DAA), the mixed solvent of 10g benzene, 10g toluene and 10g dimethylbenzene, 0.1gBPO and 0.1g dodecanoyl joins is furnished with thermometer, in the there-necked flask of electric mixer and prolong.From a mouth of plug in thermometer, pass into 2min nitrogen, make shielding gas.With water-bath heating, polymerization temperature is made to control at 85 DEG C, polyreaction 4 hours.In system, add 0.24g urotropine after polymerization terminates and carry out crosslinking reaction.
(2) saponification of multipolymer: add 75g strong aqua (mass concentration 28%) in polymerization system.Airtight stirring heating 1 hour in the water-bath of constant temperature 99 DEG C.
(3) separation of multipolymer: mixed system the most obtained left standstill after 2.5 hours, lower floor's solution is obtained by oily water separation, lower floor's solution obtains through suction filtered through kieselguhr the translucent solution that there are a small amount of oil bloom on flaxen upper strata, this solution obtains light yellow transparent solution through membrane sepn again, obtains water-soluble low cross-linking polymaleic anhydride-diisobutylene multipolymer sodium salt dispersion agent product.(weak yellow liquid, solid content 25.5%, pH value=10.8, dispersion force is 120 [mgMnO2/100ml sample solution (0.025%)], degree of crosslinking=20.3%, second-order transition temperature 80.8 DEG C)
Embodiment 6:
(1) synthesis of multipolymer: by reactant 33.6g diisobutylene, 29.4g maleic anhydride, 1.2g hydroxyethyl methylacrylate and 2.4g glycidyl methacrylate, the mixed solvent of 9g dioxan and 18g ethyl acetate, 0.08gBPO and 0.08g isopropyl benzene hydroperoxide joins is furnished with thermometer, in the there-necked flask of electric mixer and prolong.From a mouth of plug in thermometer, pass into 2min nitrogen, make shielding gas.With water-bath heating, polymerization temperature is made to control at 90 DEG C, polyreaction 5 hours.In system, 0.16g methylamine is added and 0.06 Isopropylamine carries out crosslinking reaction after polymerization terminates.
(2) saponification of multipolymer: add 33.6g potassium hydroxide 90g deionized water in polymerization system.Airtight stirring heating 1.5 hours in the water-bath of constant temperature 95 DEG C.
(3) separation of multipolymer: mixed system the most obtained left standstill after 2 hours, lower floor's solution is obtained by oily water separation, lower floor's solution obtains through suction filtered through kieselguhr the translucent solution that there are a small amount of oil bloom on flaxen upper strata, this solution obtains light yellow transparent solution through membrane sepn again, obtains water-soluble low cross-linking polymaleic anhydride-diisobutylene multipolymer sodium salt dispersion agent product.(weak yellow liquid, solid content 21.4%, pH value=11.0, dispersion force is 115 [mgMnO2/100ml sample solution (0.025%)], degree of crosslinking=18.8%, second-order transition temperature 79.6 DEG C)
Embodiment 7:
(1) synthesis of multipolymer: by reactant 33.6g diisobutylene, 29.4g maleic anhydride, 1.4gN-n-methylolacrylamide and 4.2g pentaerythritol triacrylate, the mixed solvent of 10g benzene and 25g toluene, 0.06g dodecanoyl and 0.12g isopropyl benzene hydroperoxide join is furnished with thermometer, in the there-necked flask of electric mixer and prolong.From a mouth of plug in thermometer, pass into 2min nitrogen, make shielding gas.With water-bath heating, polymerization temperature is made to control at 85 DEG C, polyreaction 5 hours.In system, 0.2g ethamine is added and 0.1g quadrol carries out crosslinking reaction after polymerization terminates.
(2) saponification of multipolymer: add 33.6g potassium hydroxide 100g deionized water in polymerization system.Airtight stirring heating 1.2 hours in the water-bath of constant temperature 97 DEG C.
(3) separation of multipolymer: mixed system the most obtained left standstill after 2.5 hours, lower floor's solution is obtained by oily water separation, lower floor's solution obtains through suction filtered through kieselguhr the translucent solution that there are a small amount of oil bloom on flaxen upper strata, this solution obtains light yellow transparent solution through membrane sepn again, obtains water-soluble low cross-linking polymaleic anhydride-diisobutylene multipolymer sodium salt dispersion agent product.(weak yellow liquid, solid content 22.5%, pH value=10.5, dispersion force is 127 [mgMnO2/100ml sample solution (0.025%)], degree of crosslinking=22.4%, second-order transition temperature 81.9 DEG C)
Embodiment 8:
(1) synthesis of multipolymer: by reactant 33.6g diisobutylene, 29.4g maleic anhydride, 0.5g hydroxyethyl methylacrylate and 2.0g glycidyl methacrylate, the solvent dioxan of 28g, 0.12g hydrogen peroxide and 0.1g isopropyl benzene hydroperoxide join is furnished with thermometer, in the there-necked flask of electric mixer and prolong.From a mouth of plug in thermometer, pass into 2min nitrogen, make shielding gas.With water-bath heating, polymerization temperature is made to control at 80 DEG C, polyreaction 4 hours.In system, add 0.16g dimethylamine after polymerization terminates and carry out crosslinking reaction.
(2) saponification of multipolymer: add 24g sodium hydroxide 60g deionized water in polymerization system.Airtight stirring heating 1 hour in the water-bath of constant temperature 99 DEG C.
(3) separation of multipolymer: mixed system the most obtained left standstill after 2 hours, lower floor's solution is obtained by oily water separation, lower floor's solution obtains through suction filtered through kieselguhr the translucent solution that there are a small amount of oil bloom on flaxen upper strata, this solution obtains light yellow transparent solution through membrane sepn again, obtains water-soluble low cross-linking polymaleic anhydride-diisobutylene multipolymer sodium salt dispersion agent product.(weak yellow liquid, solid content 23.7%, pH value=10.9, dispersion force is 112 [mgMnO2/100ml sample solution (0.025%)], degree of crosslinking=17.6%, second-order transition temperature 79.0 DEG C).
Claims (19)
1. water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, is characterized in that this dispersant system with the addition of Third monomer, achieves lightly crosslinked, is prepared by following three steps:
Step 1: by reactant diisobutylene, maleic anhydride, Third monomer, solvent and initiator join in proportion is furnished with thermometer, in the there-necked flask of electric mixer and prolong, 2min nitrogen is passed into from a mouth of plug in thermometer, make shielding gas, with water-bath heating, make polymerization temperature control at 80 ~ 90 DEG C, polyreaction 4 ~ 8 hours, adds catalyzer after polymerization terminates and carries out crosslinking reaction in system;
Step 2: add certain density alkaline solution in polymerization system, airtight stirring heating 1 ~ 1.5 hour in the water-bath of 95 ~ 99 DEG C;
Step 3: mixed system the most obtained left standstill after 2 ~ 2.5 hours, lower floor's solution is obtained by oily water separation, lower floor's solution obtains through suction filtered through kieselguhr the translucent solution that there are a small amount of oil bloom on flaxen upper strata, this solution obtains light yellow transparent solution through membrane sepn again, obtains water-soluble low cross-linking polymaleic anhydride-diisobutylene multipolymer sodium salt dispersion agent product.
2. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, it is characterized in that described product appearance is weak yellow liquid, solid content is 21.5%-26.5%, pH value is 10.5 ~ 11.2, and dispersion force is 95 ~ 130 [mgMnO
2/ 100ml sample solution (0.025%)], the degree of crosslinking of product is 16.8% ~ 22.7%, and the glass of system is 78.5 DEG C ~ 82.5 DEG C.
3. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, is characterized in that the mol ratio of maleic anhydride and diisobutylene in described dispersion agent is 1: 1.
4. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, is characterized in that organic solvent described in step 1 is the combination of one or several in benzene,toluene,xylene, ethyl acetate, dioxan.
5. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, is characterized in that the weight ratio of organic solvent described in step 1 and maleic anhydride is 1: (0.8 ~ 1.1).
6. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, to is characterized in that described in step 1 containing Third monomer being one or both in N hydroxymethyl acrylamide, diacetone-acryloamide(DAA), hydroxyethyl methylacrylate, glycidyl methacrylate, acrylate, pentaerythritol.
7. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, is characterized in that the mol ratio of Third monomer described in step 1 and maleic anhydride is for (0.05-0.1): 1.
8. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, be characterised in that used in step 1 is benzoyl peroxide, dodecanoyl, hydrogen peroxide, one or both in isopropyl benzene hydroperoxide.
9. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, is characterised in that in step 1, initiator amount is the 0.005-0.008 of maleic anhydride quality.
10. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agent and preparation method thereof, is characterised in that in step 1, polymeric reaction temperature is 80 DEG C ~ 90 DEG C.
11. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agents and preparation method thereof, are characterised in that in step 1, polymerization reaction time is 4 ~ 8 hours.
12. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agents and preparation method thereof, be characterised in that in step 1 used for catalyzer be methylamine, dimethylamine, triethylamine, ethamine, diethylamine, Isopropylamine, one or both in quadrol, urotropine.
13. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agents and preparation method thereof, be characterised in that in step 1 used for catalyst levels be 5% ~ 7% of Third monomer quality.
14. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agents and preparation method thereof, are characterised in that in step 2, the kind for saponification alkaline solution used is sodium hydroxide, potassium hydroxide, ammoniacal liquor.
15. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agents and preparation method thereof, be characterised in that in step 2 used for saponification alkaline concentration be 25%-30%, the mol ratio of alkali and maleic anhydride is 2: 1.
16. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agents and preparation method thereof, are characterised in that in step 2, saponification reaction temperature used is 95 DEG C ~ 99 DEG C.
17. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agents and preparation method thereof, are characterised in that in step 2, saponification time used is 1 ~ 1.5 hour.
18. one according to claim 1 water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agents and preparation method thereof, are characterised in that membranous type used in step 3 number is by ceramic membrane device, and the membranous type number selected is JWCM07*30.
19. one water-soluble low cross-linking polymaleic anhydride-diisobutylene copolymer salt dispersion agents according to claim 1 or 2 ~ 18 and preparation method thereof, is characterized in that described dispersion agent can be used for solution polymerized butadiene styrene rubber dispersion technology, coating dispersion, leather retanning agent dispersion technology field.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966737A (en) * | 2016-01-13 | 2017-07-21 | 苏州纳朴材料科技有限公司 | The dispersant and its application method of a kind of aqueous-based ceramic slurry |
| CN114933669A (en) * | 2022-07-04 | 2022-08-23 | 宜兴市湖景化工有限公司 | Preparation method of dispersing force adjustable sodium polycarboxylate dispersant for rubber |
| CN118184866A (en) * | 2024-04-07 | 2024-06-14 | 宜兴市湖景化工有限公司 | Preparation method and application method of polycarboxylic acid sodium salt dispersing agent with adjustable dispersing force for rubber |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5480136A (en) * | 1977-12-09 | 1979-06-26 | Hitachi Ltd | Heat sensitive recording sheet and production of the same |
| CN102532382A (en) * | 2011-12-12 | 2012-07-04 | 东营黎宁化工有限公司 | Preparation method of polydiisobutylene-fatty monoamide maleate-acrylic acid leather retanning-fatting agent |
-
2015
- 2015-10-12 CN CN201510660745.5A patent/CN105131162A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5480136A (en) * | 1977-12-09 | 1979-06-26 | Hitachi Ltd | Heat sensitive recording sheet and production of the same |
| CN102532382A (en) * | 2011-12-12 | 2012-07-04 | 东营黎宁化工有限公司 | Preparation method of polydiisobutylene-fatty monoamide maleate-acrylic acid leather retanning-fatting agent |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106966737A (en) * | 2016-01-13 | 2017-07-21 | 苏州纳朴材料科技有限公司 | The dispersant and its application method of a kind of aqueous-based ceramic slurry |
| CN114933669A (en) * | 2022-07-04 | 2022-08-23 | 宜兴市湖景化工有限公司 | Preparation method of dispersing force adjustable sodium polycarboxylate dispersant for rubber |
| CN118184866A (en) * | 2024-04-07 | 2024-06-14 | 宜兴市湖景化工有限公司 | Preparation method and application method of polycarboxylic acid sodium salt dispersing agent with adjustable dispersing force for rubber |
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