CN103897089B - Low viscous modified polyvinyl alcohol of a kind of crystalloid and preparation method thereof - Google Patents
Low viscous modified polyvinyl alcohol of a kind of crystalloid and preparation method thereof Download PDFInfo
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Abstract
The invention discloses the preparation method of the low viscous modified polyvinyl alcohol of a kind of crystalloid, comprise: A) modification polyvinyl acetate technique, B) twice alcoholysis: described modification polyvinyl acetate 1000 parts is put into whipping device, start to stir, control stirring velocity is 30-60 rev/min, then gradation adds sodium hydrate methanol solution 10-200 part that mass concentration is 4%-6%, under the condition of 30 DEG C-50 DEG C, react 0.5-3 hour; There is solvent to separate out after having reacted, obtain solidliquid mixture; C) centrifugation and drying process.The present invention is for the sodium allyl sulfonate of low-viscosity and vinyl acetate resin copolymer, and adopt twice alcoholysis process to manufacture crystalloid modified polyvinyl alcohol, in production process, product loss is few, and product yield is high.
Description
Technical field
The invention belongs to chemical technology field, relate to the preparation method of modified polyvinyl alcohol (PVA).
Background technology
Polyvinyl alcohol (PVA) is a kind of important water-soluble high-molecular compound grown up early 1950s.Application is very extensive, can be used to producd fibers, also can be used as chemical & blended fabric slurry, coating, tackiness agent, emulsifying agent, papermaking processing aid etc.Along with the development of science and technology, day by day urgent to the demand of different viscosity, different alcoholysis degree polyvinyl alcohol (PVA).Find out from a lot of research both domestic and external, polyvinyl alcohol (PVA) product is to height two poles development, and namely viscosity and alcoholysis degree develop to higher and lower both direction.Polyvinyl alcohol (PVA) product of these different viscositys and alcoholysis degree has property, high added value and feature in short supply, and (PVA) of low-viscosity and low alcoholysis level is except the general characteristic (as solvability under water absorbability, ventilation property, nontoxicity, high temperature is stablized) with conventional polyvinyl alcohol (PVA), also there is the advantages such as solvability in cold water is good, biodegradable, therefore, purposes is widely had, as industries such as paper conversion, tamanori, coating, film, medicine, makeup in non-fiber.Particularly temperature-sensitive paper processing aspect, needs soluble in water, easy dyeing and acid-fast dispersion agent.
Because vinyl alcohol can not with unbound state stable existence, polyvinyl alcohol (PVA) can not directly obtain from vinyl alcohol polymerization, the polyvinyl acetate that adopts carries out alcoholysis to prepare more under base catalysis at present, namely for preparing the polyvinyl alcohol (PVA) of low-viscosity, the polyvinyl acetate of low-viscosity must first be prepared.
In order to improve the use properties of polyvinyl alcohol product, in solution polymerization, adding the second polymerization single polymerization monomer carry out graft copolymerization, make polyvinyl acetate molecular chain introduce second comonomer.Carry out the polyvinyl alcohol that modification is prepared in alcoholysis again.Patent application 201110086949.4 discloses a kind of preparation method of carboxyl acid modified polyvinyl alcohol, and what this patent application stressed is carboxyl acid modified.Patent application 201110152874.5 discloses a kind of preparation method of aldehyde radical modified polyvinyl alcohol, and what this application stressed is aldehyde radical modification, institute's production low viscosity product, and product is Powdered.According to present standard and custom, viscosity is conventional products at 15-50mPa.s, and viscosity is greater than 50mPa.s and is called high viscosity, and viscosity is called low viscosity lower than 10mPa.s.
The product difficulty of existing low-viscosity is shaping, the yield of product is low, a large amount of powder that existing powdery product produces enter in solvent, owing to containing moisture in solvent, in separated from solvent process, powder dissolution is finally discharged along with waste water in water and loses, and not only pollute environment but also have lost product, economic benefit is low.
About production unit, cotton-shaped polyvinyl alcohol can be produced with the high-alkali alcoholysis method of twin screw alcoholysis machine in prior art, in production process, carry out mechanical disintegration.Can production sheet polyvinyl alcohol with belt alcoholysis machine low alkalinity alcoholysis, carry out mechanical disintegration in production process.
Summary of the invention
The object of the invention is to overcome deficiency of the prior art, and low viscous modified polyvinyl alcohol of a kind of crystalloid and preparation method thereof be provided, the method by properties-correcting agent and vinyl acetate resin graft copolymerization, then by multipolymer alcoholysis.Method of the present invention, technique is simple, and do not need mechanical disintegration, product is crystalloid, and effectively can solve the defect of low viscosity powdery product in prior art.In addition, carry out the modified polyvinyl alcohol of modified manufacture with sodium allyl sulfonate, containing sulfonic acid group in its molecular structure, as the dispersion agent of thermal printing paper, there is polymolecularity; Easy colouring, the features such as image persistence can be kept.
For achieving the above object, the technical solution used in the present invention is:
A preparation method for the low viscous modified polyvinyl alcohol of crystalloid, specifically comprises the following steps:
(1) modification polyvinyl acetate is prepared;
(2) described modification polyvinyl acetate 1000 parts is put into whipping device, start to stir, control stirring velocity is 30-60 rev/min, then adds sodium hydrate methanol solution 10-200 part that mass concentration is 4%-6%, under the condition of 30 DEG C-50 DEG C, reacts 0.5-3 hour; There is solvent to separate out after having reacted, obtain solidliquid mixture; Described sodium hydrate methanol solution adds at twice, and add-on is 0.8-1.2:1 with the ratio of second time add-on for the first time, and when reaction starts, first time adds, and reacts second time after 40-50 minute and adds;
(3) by described solidliquid mixture centrifugation, dry crystalline product.
Described in step (1), the concentration of modification polyvinyl acetate is preferably 40%-50%.
Stopper described in step (1) is preferably sulphur fork pentanoic.
The concrete steps of step (1) are preferably, by weight, with 500-1500 part methyl alcohol for solvent, 1-3 part Diisopropyl azodicarboxylate is initiator, under the condition of 60 DEG C-65 DEG C, 1000 parts of vinyl acetate resins and 1-50 part properties-correcting agent carry out copolyreaction, add 0.05-0.1 part stopper termination reaction after reaction times 3-6 hour, remove unreacted vinyl acetate resin, product with methylalcohol dissolves, and mass concentration is adjusted to 20%-50%, obtain modification polyvinyl acetate.
Described in step (1), properties-correcting agent is sodium allyl sulfonate or sodium vinyl sulfonate.
By containing sulfonic acid group in the polyvinyl alcohol molecule chain that sodium allyl sulfonate modification is obtained, for temperature-sensitive paper inductive layer and printing ink jetting paper, according to there being polymolecularity; Easy colouring, image persistence can be kept, the feature such as make fiber staining firm, as special dispersion agent and colloid protective agent.
Described in step (2), the add-on of modification polyvinyl acetate is no more than 60% of kneader volume, prevents from overflowing because of the expansion of reactant in reaction process.
Described in step (2), sodium hydrate methanol solution preferably adds at twice, and add-on is 0.8-1.2:1 with the ratio of second time add-on for the first time, and when reaction starts, first time adds, and reacts second time after 40-50 minute and adds.
The concrete steps of step (3) are preferably: by described solidliquid mixture centrifugation 2-8 minute, the product after centrifugation is vacuum-drying 1-3 hour under the condition of 65 DEG C-102 DEG C, and dried product is crystalloid.
The alcoholysis degree of step (3) described crystalline product is 80-99 % by mole, and the observed value of 4% Aqueous Solution Viscosity rotational viscosimeter is 2.0-5.0mPa.s.
A kind of low viscous modified polyvinyl alcohol, alcoholysis degree is 80-99 % by mole, and the observed value of 4% Aqueous Solution Viscosity rotational viscosimeter is 2.0-5.0mPa.s, and described polyvinyl alcohol is crystalloid product.
The present invention will be further explained below.
Crystalloid of the present invention is the powdery product after being different from mechanical disintegration, is a kind ofly to be similar to the thing shape after substance crystallization.
In the alcoholysis process of polyvinyl acetate, except there is chemical transformation, also along with the change of phase, material is solid phase by original liquid phase, in its phase transition process, viscosity can rise significantly and then reduce (being called gelation) fast, and the time is between 1-30 minute.In order to overcome the disadvantageous effect that gelation brings, just need a kind of whipping appts, and kneader just in time has this function.
Sodium allyl sulfonate modification polyvinyl acetate speed of reaction when alcoholysis of low-viscosity is too fast, and product just becomes very tiny powder, and speed of reaction crosses that slow then production efficiency is low.The factor affecting speed of reaction responds temperature, the add-on of sodium hydroxide and stir speed (S.S.).Stir speed (S.S.) is too fast, and the particle of product is just little.Under certain temperature of reaction, substep adds sodium hydroxide just can reach the object controlling speed of response, thus controls the final form of product.
Compared with prior art, advantage of the present invention is:
1. method of the present invention, technique is simple, and do not need mechanical disintegration, product is crystalloid.
2. in production process, product loss is few, and product yield is high, when effectively can solve production low viscosity product in prior art, product is not easily shaped, and mostly is very tiny powder, and a large amount of powder enters in waste liquid, the problems such as not easily separated, product yield is low, powder contamination environment.
3. the waste liquid no suspended substance adopting method of the present invention to produce, is convenient to reclaim.
4. carry out the modified polyvinyl alcohol of modified manufacture with sodium allyl sulfonate, containing sulfonic acid group in its molecular structure, as the dispersion agent of thermal printing paper, there is polymolecularity; Easy colouring, the features such as image persistence can be kept.
Embodiment
Below by embodiment, the present invention is specifically described; what be necessary to herein means out is that following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment according to foregoing invention content to the present invention.
The method that viscosity specifies according to GB/T12010.2-2010 annex E measures.
The method that alcoholysis degree specifies according to GB/T12010.2-2010 Appendix D measures.
Yield refers to the products in kind amount (deduction impurity and volatile matter) of each experiment and the ratio of theoretical yield.
The solid content measuring method of waste liquid: take waste liquid 10-20 gram (being accurate to 0.0001 gram) with flat type weighing bottle, the baking oven putting into 100-105 DEG C is dried to constant weight, then weighs.Non-volatile matter quality in weighing bottle and the waste liquid mass ratio taken are called the solid content of waste liquid.
The model SH--5 type of kneader described in embodiment, Nanjing ENSO scientific & technical corporation produces.
Embodiment 1
In 5 liters of double-layer glass reaction kettles with distillation and reflux, put into methyl alcohol 1600 grams, sodium allyl sulfonate 60 grams, vinyl acetate resin 2000 grams, is warming up to 65 DEG C in still after nitrogen replacement, then adds Diisopropyl azodicarboxylate 2 grams, opens and stirs, react 4 hours.Add 0.1g stopper termination reaction, be warming up to 80 DEG C and allow still internal solvent volatilize, methyl alcohol is added in midway makes for 3-5 time unreacted vinyl acetate resin in still evaporate completely.Then be cooled to 40 DEG C, then add methyl alcohol about 1500 grams product is dissolved, and concentration is adjusted to 40%.
Above-mentioned product 1000 parts is put into kneader, and (total amount is no more than 60% of volume, reactant is avoided to overflow), temperature of reaction is 45 DEG C, open and stir, stirring velocity 30 revs/min, first put into the sodium hydrate methanol solution 30 parts of 5%, react the sodium hydrate methanol solution 30 parts again putting into 5% after 40 minutes.Continue stirring to stop after 60 minutes, have solvent to separate out after having reacted, reactant becomes solid-liquid mixtures.
Solid-liquid mixtures is poured out from kneader and puts into whizzer, be separated 5 minutes with the centrifugation of 3000 revs/min, the product after centrifugation is taken out the dry 1-3 hour of vacuum drying oven putting into 65 DEG C-102 DEG C, obtain crystalloid product.After testing: alcoholysis degree 90.4 % by mole, viscosity 4.0mPa.s.
Embodiment 1 product yield is 99.96%, and the solid content in waste liquid is less than 0.005%, (and the solid content in prior art in waste liquid is generally in scope of 0.05-0.40%, has suspended substance).
Embodiment 2
Methyl alcohol 2000 grams is put into, sodium allyl sulfonate 100 grams, vinyl acetate resin 2000 grams in 5 liters of double-layer glass reaction kettles with distillation and reflux, 65 DEG C are warming up to after nitrogen replacement in still, add Diisopropyl azodicarboxylate 2.2 grams again, open and stir, react 5 hours.Add 0.1g stopper termination reaction, be warming up to 80 DEG C and allow still internal solvent volatilize, methyl alcohol is added in midway makes for 3-5 time unreacted vinyl acetate resin in still evaporate completely.Then be cooled to 40 DEG C, then add methyl alcohol about 1500 grams product is dissolved, and concentration is adjusted to 40%.
Above-mentioned product 1000 parts is put into kneader (total amount is no more than 60% of volume), temperature of reaction is 45 DEG C, open and stir, stirring velocity 40 revs/min, first put into the sodium hydrate methanol solution 40 parts of 5%, react the sodium hydrate methanol solution 30 parts again putting into 5% after 40 minutes.Continue stirring to stop after 30 minutes, have solvent to separate out after having reacted, reactant becomes solid-liquid mixtures.
Solid-liquid mixtures is poured out from kneader and puts into whizzer, be separated 5 minutes with the centrifugation of 3000 revs/min, the product after centrifugation is taken out the dry 1-3 hour of vacuum drying oven putting into 65 DEG C-102 DEG C, obtain crystalloid product.After testing: alcoholysis degree 81.8 % by mole, viscosity 2.1mPa.s.
Embodiment 2 product yield is 99.92%, and the solid content of waste liquid is less than 0.005%, (and in prior art, the solid content of waste liquid, generally in the scope of 0.05-0.40%, has suspended substance).
Embodiment 3
In 5 liters of double-layer glass reaction kettles with distillation and reflux, put into methyl alcohol 1600 grams, sodium allyl sulfonate 60 grams, vinyl acetate resin 2000 grams, is warming up to 65 DEG C in still after nitrogen replacement, then adds Diisopropyl azodicarboxylate 2 grams, opens and stirs, react 6 hours.Add 0.1g stopper termination reaction, be warming up to 80 DEG C and allow still internal solvent volatilize, methyl alcohol is added in midway makes for 3-5 time unreacted vinyl acetate resin in still evaporate completely.Then be cooled to 40 DEG C, then add methyl alcohol about 1500 grams product is dissolved, and concentration is adjusted to 40%.
Above-mentioned product 1000 parts is put into kneader (total amount is no more than 60% of volume), temperature of reaction is 35 DEG C, open and stir, stirring velocity 60 revs/min, first put into the sodium hydrate methanol solution 40 parts of 5%, react the sodium hydrate methanol solution 50 parts again putting into 5% after 40 minutes.Continue stirring to stop after 80 minutes, have solvent to separate out after having reacted, reactant becomes solid-liquid mixtures.
Solid-liquid mixtures is poured out from kneader and puts into whizzer, be separated 5 minutes with the centrifugation of 3000 revs/min, the product after centrifugation is taken out the dry 1-3 hour of vacuum drying oven putting into 65 DEG C-102 DEG C, obtain crystalloid product.After testing: alcoholysis degree 98.6 % by mole, viscosity 4.5mPa.s.
Embodiment 3 product yield is 99.95%, and no suspended substance in waste liquid (methyl alcohol), the solid content of waste liquid is less than 0.005%, (and in prior art, the solid content of waste liquid, generally in the scope of 0.05-0.40%, has suspended substance).
Embodiment 4
1. in 5 liters of double-layer glass reaction kettles with distillation and reflux, put into methyl alcohol 1600 grams, 30 grams, acetaldehyde, vinyl acetate resin 2000 grams, is warming up to 65 DEG C in still after nitrogen replacement, then adds Diisopropyl azodicarboxylate 2 grams, opens and stirs, react 6 hours.Add 0.1g stopper termination reaction, be warming up to 80 DEG C and allow still internal solvent volatilize, methyl alcohol is added in midway makes for 3-5 time unreacted vinyl acetate resin in still evaporate completely.Then be cooled to 40 DEG C, then add methyl alcohol about 1500 grams product is dissolved, and concentration is adjusted to 40% (this product is divided into two portions, and a part carries out alcoholysis by secondary alcoholysis method, and alcoholysis is carried out in another part alcoholysis).
Above-mentioned product 1000 parts is put into kneader (total amount is no more than 60% of volume), temperature of reaction is 35 DEG C, open and stir, stirring velocity 60 revs/min, first put into the sodium hydrate methanol solution 40 parts of 5%, react the sodium hydrate methanol solution 50 parts again putting into 5% after 40 minutes.Continue stirring to stop after 80 minutes, have solvent to separate out after having reacted, reactant becomes solid-liquid mixtures.
Solid-liquid mixtures is poured out from kneader and puts into whizzer, be separated 5 minutes with the centrifugation of 3000 revs/min, the product after centrifugation is taken out the dry 1-3 hour of vacuum drying oven putting into 65 DEG C-102 DEG C, obtain crystalloid product.After testing: alcoholysis degree 98.6 % by mole, viscosity 5.0mPa.s.
Embodiment 4.1 product yield is 99.95%, and no suspended substance in waste liquid (methyl alcohol), the solid content of waste liquid is less than 0.005%, (and in prior art, the solid content of waste liquid, generally in the scope of 0.05-0.40%, has suspended substance).
2. again another part product 1000 parts is put into kneader (total amount is no more than 60% of volume), temperature of reaction is 35 DEG C, open and stir, stirring velocity 60 revs/min, first put into the sodium hydrate methanol solution 90 parts of 5%, stir after 80 minutes and stop, having solvent to separate out after having reacted, reactant becomes solid-liquid mixtures.
Solid-liquid mixtures is poured out from kneader and puts into whizzer, be separated 5 minutes with the centrifugation of 3000 revs/min, the product after centrifugation is taken out the dry 1-3 hour of vacuum drying oven putting into 65 DEG C-102 DEG C, obtain the product of yellow powder.After testing: alcoholysis degree 98.6 % by mole, viscosity 5.0mPa.s.
Embodiment 4.2 product yield is 98.15%, has suspended substance in waste liquid (methyl alcohol), and the solid content of waste liquid is 0.45%.
Embodiment 4.1 has also produced crystalloid modified polyvinyl alcohol, but does not have sulfonic acid group in molecular structure, and therefore product does not have the performance of product in embodiment 1-3.
Embodiment 5
Getting the polymerization degree is that about 500-1000 (unmodified) polyvinyl acetate 1000 parts puts into kneader (total amount is no more than 60% of volume), temperature of reaction is 35 DEG C, open and stir, stirring velocity 60 revs/min, first put into the sodium hydrate methanol solution 40 parts of 5%, react the sodium hydrate methanol solution 50 parts again putting into 5% after 40 minutes.Continue stirring to stop after 80 minutes, have solvent to separate out after having reacted, reactant becomes solid-liquid mixtures.
Solid-liquid mixtures is poured out from kneader and puts into whizzer, 5 minutes are separated with the centrifugation of 3000 revs/min, product after centrifugation is taken out the dry 1-3 hour of vacuum drying oven putting into 65 DEG C-102 DEG C, obtain the product of crystalloid (granular).After testing: alcoholysis degree 97.6 % by mole, viscosity 6.1mPa.s.
Embodiment 5 product yield is 99.95%, and no suspended substance in waste liquid (methyl alcohol), the solid content of waste liquid is less than 0.005%, (and in prior art, the solid content of waste liquid, generally in the scope of 0.05-0.40%, has suspended substance).
Embodiment 5 has also manufactured crystalloid polyvinyl alcohol product, but does not have sulfonic acid group in molecular structure, and therefore product does not have the performance of product in embodiment 1-3.
Claims (4)
1. a preparation method for the low viscous modified polyvinyl alcohol of crystalloid, is characterized in that, specifically comprise the following steps:
(1) modification polyvinyl acetate is prepared: by weight, with 500-1500 part methyl alcohol for solvent, 1-3 part Diisopropyl azodicarboxylate is initiator, under the condition of 60 DEG C-65 DEG C, 1000 parts of vinyl-acetic esters and 1-50 part properties-correcting agent carry out copolyreaction, add 0.05-0.1 part stopper termination reaction after reaction times 3-6 hour, remove unreacted vinyl-acetic ester, product with methylalcohol dissolves, and mass concentration is adjusted to 20%-50%, obtains modification polyvinyl acetate; Described properties-correcting agent is sodium allyl sulfonate or sodium vinyl sulfonate; Described stopper is sulphur fork pentanoic;
(2) described modification polyvinyl acetate 1000 parts is put into whipping device, start to stir, control stirring velocity is 30-60 rev/min, then adds sodium hydrate methanol solution 10-200 part that mass concentration is 4%-6%, under the condition of 30 DEG C-50 DEG C, reacts 0.5-3 hour; There is solvent to separate out after having reacted, obtain solidliquid mixture; Described sodium hydrate methanol solution adds at twice, and add-on is 0.8-1.2:1 with the ratio of second time add-on for the first time, and when reaction starts, first time adds, and reacts second time after 40-50 minute and adds; Described whipping device is kneader, and the add-on of described modification polyvinyl acetate is no more than 60% of kneader volume;
(3): by described solidliquid mixture centrifugation 2-8 minute, the product after centrifugation is vacuum-drying 1-3 hour under the condition of 65 DEG C-102 DEG C, and dried product is crystalloid; The alcoholysis degree of described crystalline product is 80-99 % by mole, and the observed value of 4% Aqueous Solution Viscosity rotational viscosimeter is 2.0-5.0mPa.s.
2. the preparation method of the low viscous modified polyvinyl alcohol of crystalloid according to claim 1, it is characterized in that, described in step (1), the mass concentration of modification polyvinyl acetate is 40%-50%.
3. the preparation method of the low viscous modified polyvinyl alcohol of crystalloid according to claim 1 or 2, it is characterized in that, described in step (2), sodium hydrate methanol solution adds at twice, add-on is 1:1 with the ratio of second time add-on for the first time, when reaction starts, first time adds, and reacts second time after 45 minutes and adds.
4. the low viscous modified polyvinyl alcohol of crystalloid prepared of the preparation method of the low viscous modified polyvinyl alcohol of crystalloid according to claim 1, alcoholysis degree is 80-99 % by mole, the observed value of 4% Aqueous Solution Viscosity rotational viscosimeter is 2.0-5.0mPa.s, it is characterized in that, described polyvinyl alcohol is crystalloid product.
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| CN104530277A (en) * | 2014-11-25 | 2015-04-22 | 湖南省湘维有限公司 | Polyvinyl alcohol and preparation method thereof |
| CN107920528A (en) * | 2015-09-04 | 2018-04-17 | 住友化学株式会社 | Composition, the manufacture method of composition and composition pesticide |
| CN105713120A (en) * | 2016-04-29 | 2016-06-29 | 安徽皖维高新材料股份有限公司 | Method for crushing polyvinyl alcohol |
| CN106188354B (en) * | 2016-08-10 | 2018-10-30 | 安徽皖维高新材料股份有限公司 | A kind of preparation method of the polyvinyl alcohol dispersant with high efficiency dispersion stability |
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| CN100365033C (en) * | 2004-09-02 | 2008-01-30 | 北京东方石油化工有限公司有机化工厂 | Method for synthesizing high solid content vinyl acetate-ethylene copolymer emulsion |
| DE102005054913A1 (en) * | 2005-11-17 | 2007-05-24 | Wacker Polymer Systems Gmbh & Co. Kg | Silane-modified polyvinyl alcohols |
| ES2361642T3 (en) * | 2008-06-23 | 2011-06-20 | Wacker Chemie Ag | POLYMERIC DISPERSION IN HEAT RESISTANT EMULSION. |
| CN101747459B (en) * | 2008-12-02 | 2011-09-07 | 卢金永 | Preparation method of dispersing agent of chemically modified polyvinyl alcohol |
| CN102127177A (en) * | 2010-11-11 | 2011-07-20 | 云南煤化工应用技术研究院 | Low-alcoholysis-degree polyvinyl acetate (PVA) continuous alcoholysis process |
| CN102108107A (en) * | 2011-01-21 | 2011-06-29 | 湖南省湘维有限公司 | Method for preparing polyvinyl alcohol with low polymerization degree |
| CN102731710B (en) * | 2011-04-07 | 2015-03-04 | 中国石油化工集团公司 | Carboxyl modified polyvinyl alcohol and method for preparing same |
| CN102311516B (en) * | 2011-06-09 | 2013-05-22 | 天津辛德玛悬浮剂有限公司 | Method for preparing PVA (polyvinyl alcohol) assisted dispersant for manufacturing polyvinyl chloride by using suspension method |
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