CN102344511B - Modified synthesis method for high-viscosity film forming resin with dielectric property - Google Patents
Modified synthesis method for high-viscosity film forming resin with dielectric property Download PDFInfo
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- CN102344511B CN102344511B CN 201010245831 CN201010245831A CN102344511B CN 102344511 B CN102344511 B CN 102344511B CN 201010245831 CN201010245831 CN 201010245831 CN 201010245831 A CN201010245831 A CN 201010245831A CN 102344511 B CN102344511 B CN 102344511B
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Abstract
The present invention relates to a modified synthesis method for a high-viscosity film forming resin with dielectric property. According to the method, ultrahigh polymerization degree and fiber-grade polyvinyl alcohol is adopted as a raw material; dimethyl sulfoxide is adopted a cosolvent and a reaction solvent, wherein the cosolvent and the reaction solvent are adopted for the polyvinyl alcohol solution and acrylonitrile; the polyvinyl alcohol is dissolved, and is fused with the reaction solvent; the acrylonitrile is added, and the polyvinyl alcohol is subjected to an etherification modification reaction in a molten liquid and homogeneous system under a catalytic action through sodium hydroxide to synthesize a high-viscosity, high-dielectric constant and hydrophobic cyanoethyl etherate; the post refining treatment is performed to obtain the product, wherein the substitution degree of the product is more than 90%, the maximum dielectric constant epsilon is 15-16, the product becomes the upgrade and update product of the traditional film forming material with the dielectric property.
Description
Technical field
The present invention relates to a kind of modification synthetic method that possesses the high viscosity film-forming resin of dielectricity, be as raw material with the superelevation polymerization degree, fibre-grade polyvinyl alcohol, select dimethyl sulfoxide (DMSO) as cosolvent and the process solvent of polyvinyl alcohol solution and vinyl cyanide, with miscible with dimethyl sulfoxide (DMSO) after the polyvinyl alcohol water dissolution, add sodium hydroxide and vinyl cyanide in fused solution and homogeneous system to polyvinyl alcohol in hydroxyl carry out the synthetic method of etherificate, the cyanoethyl etherate that obtains through synthetic method modification of the present invention has possessed high viscosity, high substitution value, high-k and hydrophobic nature.
Technical background
Polyvinyl alcohol (PVA) is a kind of broad-spectrum high molecular weight water soluble polymer, also is one of best film-forming resin.Its dielectric properties are higher.Because polyvinyl alcohol has moisture absorption, therefore the water tolerance after the film forming and poor stability have influenced the use aspect electric.
Polyvinyl alcohol and vinyl cyanide adopt the Michael addition polymerization process, to on the polyvinyl alcohol molecular chain main chain and side group on hydroxyl carry out etherification modified, in conjunction with last hydrophobic cyano group, the cyanoethyl etherate that obtains, kept the good film-forming properties of polyvinyl alcohol, reduced water-soluble.
The size of the specific inductivity of polymkeric substance, the polar molecule that depends on polarization situation.The polarity of molecule is more strong, degree of polarization is more big, then specific inductivity also more big cyano group be the strong polar molecule of polarity, cyano group is in the side group position and more is conducive to oriented polarization generation moment of dipole than on main chain, cyano group is the functional group with big moment of dipole, along with the raising of cyano group substitution value, through the cyanoethyl etherate after etherification modified, possessed the high and big feature of moment of dipole of polarization density, become the polymkeric substance of high-k.Be novel hydrophobic nature, the film forming material of high dielectric property.
It is a lot of at present both at home and abroad polyvinyl alcohol to be carried out the etherification modified synthetic method of cyanoethyl, all has some improvement at aspects such as dielectricity, water tolerance.
Patent CN1528799A report adopts the polyvinyl alcohol of the polymerization degree 600～2000, partial alcoholysis degree (non-fibre-grade) to do raw material under base catalysis, directly uses the cyanoethyl ether-β-polyvinyl alcohol of vinyl cyanide etherification reaction preparation, the purity height of product, good insulating.But because this synthetic method is the out-phase building-up reactions of carrying out under anhydrous non-fused solution prerequisite, vinyl cyanide is reactant, is again the solvent of product.Have only when the product dissolving on surface is left away, reaction could be from outward appearance to inner essence.Surfactivity according to polyvinyl alcohol improves along with alcoholysis degree descends, the characteristic that reduces along with the rising of the polymerization degree, and the polymerization degree and alcoholysis degree are crossed the low or too high difficulty synthetic to its modification that all can strengthen.Therefore, adopt this method that the superelevation polymerization degree of surfactivity extreme difference, the polyvinyl alcohol of complete alcoholysis level (fibre-grade) are carried out the out-phase etherification reaction, the substitution value of products obtained therefrom and homogeneity are all very limited.
In addition, the character of polyvinyl alcohol mainly is to be decided by its polymerization degree and alcoholysis degree, and the polymerization degree, alcoholysis degree are more high, and bonding strength is more strong, and film forming properties is more good, and the tensile strength of film raises with the polymerization degree, alcoholysis degree and strengthens.Therefore, with the product after above-mentioned raw materials and the method modification, viscosity number is lower, and adhesiveproperties is relatively poor, needs to unite other full-bodied materials in actual applications and just can reach bonding requirements.The thicknesses of layers of finished product is big, and the mechanical property of film and decreasing insulating do with it that the tamanori yield that base material makes is low, cost is high, and the practice category is very little.Wherein, because on the molecular chain of partial alcoholysis level polyvinyl alcohol, also there are a large amount of carboxyls etc. outward in hydroxyl-removal, therefore in to its modified-reaction process, can produce multinomial impurity, influence substitution value and the purity of product.
" dielectric properties of cyanoethylation polyvinyl alcohol " (" Dielectric Properties of Cyanoethylated Polyvinyl Alcohol " of compiling such as Xu Ming, International Paper 2006,25 (3) 4-7) adopt water and acetone soln as polyvinyl alcohol solvating agent and reaction medium, synthetic through highly basic and TBAB catalysis and vinyl cyanide low temperature etherificate under fused solution, the cyanoethylation polyvinyl alcohol that obtains, because water is to the Decomposition of vinyl cyanide in the W-response process, make reaction efficiency low, the substitution value of product is low, and yield is low, cost is high.And long reaction time, equipment has high input, the difficulty height of control reaction conditions.
Summary of the invention
The purpose of this invention is to provide a kind of with the superelevation polymerization degree, fibre-grade polyvinyl alcohol as raw material, and adjust synthesis path at its characteristics, in the reaction conditions that is fit to and reaction system, it is carried out the etherification modified synthetic method of cyanoethyl.Improved the efficient of building-up reactions, made the product after the modification, purity and substitution value height, impurity are few, viscosity number and specific inductivity are big.The characteristic that has kept the raw material high-adhesive-strength can single component be used as the tamanori base mateiral, has reduced use cost, and the thicknesses of layers of finished product is little, and the mechanical property of film and dielectric properties are good, and stability is strong.Enlarge product and used the field.Overcome the product defects that the deficiency because of above-mentioned synthetic method causes.
All polyvinyl alcohol modifications are all relevant with its hydroxyl.The degree difference that polyvinyl alcohol is replaced by hydroxyl by the acetoxy group in the macromole can be divided into complete alcoholysis level and partial alcoholysis level two big classes (fibre-grade and non-fibre-grade).Principle of the present invention and reaction system be the hydroxyl relative saturation that utilizes in the fibre-grade polyvinyl alcohol macromole, at utmost reduced the ratio that other groups on the molecular chain participate in reaction, is conducive to improve the purity of product after cyano group substitution value and the modification.Because the hydroxyl of raw material self is tending towards saturated, form hydrogen bond easily mutually, to its dissolving molecular chain is stretched by water, surfactivity increases, quote and have dimethyl sulfoxide (DMSO) that hydrogen bond destroys function as process solvent, weaken the HYDROGEN BOND INTENSITY between molecular chain, thereby open crystallizing field structure closely, making the cyano group that participates in reaction enter crystallizing field smoothly is combined with hydroxyl, improve vinyl cyanide to the etherification reaction efficient of hydroxyl, especially to the less etherificate that directly enters the hydroxyl of germ nucleus of side group upper volume, has bigger meaning.Taked the miscible method of polyvinyl alcohol solution and reaction solvent, synthetic is to carry out in fused solution and homogeneous system, makes reaction more fully, evenly.Superelevation polymerization degree raw material has also guaranteed high viscosity and the high-adhesive-strength of modification after product simultaneously.
Synthetic method of the present invention is as raw material with the superelevation polymerization degree, fibre-grade polyvinyl alcohol, select dimethyl sulfoxide (DMSO) as cosolvent and the process solvent of polyvinyl alcohol solution and vinyl cyanide, with miscible with dimethyl sulfoxide (DMSO) after the polyvinyl alcohol water dissolution, add sodium hydroxide and vinyl cyanide in fused solution and homogeneous system to polyvinyl alcohol in hydroxyl carry out the synthetic method of etherificate, synthesize the cyanoethyl etherate.
The present invention selects feature of raw material to be the polymerization degree between 2400～3500, alcoholysis degree at the polyvinyl alcohol more than 98% as raw material (the Japanese Kuraray PVA-124 of company, 135).
Concrete synthesis step is that polyvinyl alcohol is soluble in water, according to polyvinyl alcohol solution: dimethyl sulfoxide solvent=1: 2～3 volumetric ratios and dimethyl sulfoxide (DMSO) stir miscible after, add 10% sodium hydroxide solution that accounts for polyvinyl alcohol quality 6%～9%, again according to polyvinyl alcohol: the weight ratio of vinyl cyanide=1: 16～18 adds vinyl cyanide, reacts 2～5h under 45 ℃ or 70 ℃ of stationary temperature conditions.The present invention adopts a step constant temperature synthesis method.
Because the superelevation polymerization degree, fibre-grade polyvinyl alcohol are difficult to directly be dissolved in dimethyl sulfoxide (DMSO).The present invention elder generation water is dissolved into the aqueous solution with polyvinyl alcohol under 90 ℃～95 ℃ conditions, polyvinyl alcohol solution optimal dissolution degree is 15%～20%.Dimethyl sulfoxide (DMSO) is as cosolvent and the process solvent of polyvinyl alcohol solution and vinyl cyanide, because dimethyl sulfoxide (DMSO) and water and other organic solvents have mutual solubility, it is the process solvent during good acrylonitrile polymerization reacts, can accelerate alcohols cyanoethylation speed, reduce the side reaction thing and generate, improve yield.The method that the present invention adds dimethyl sulfoxide (DMSO) is to add dimethyl sulfoxide (DMSO) after the polyvinyl alcohol solution temperature is down to 40 ℃.Polyvinyl alcohol solution and dimethyl sulfoxide (DMSO) blending means are to mix under 90 ℃ of conditions of temperature, and the constant temperature churning time is no less than 30min.
The present invention is to be catalyzer with sodium hydroxide, when adding, want the temperature of attentive response solvent, if under the too high situation of temperature, add, polyvinyl alcohol can produce the saponification gelatin phenomenon, so be that the temperature of polyvinyl alcohol solution and dimethyl sulfoxide (DMSO) mixing liquid is down to below 40 ℃ in the actually operating, adopt the mode that at the uniform velocity splashes into that sodium hydroxide solution is joined in the mixing solutions.
The present invention be with vinyl cyanide as etherifying agent, according to polyvinyl alcohol: the weight ratio of vinyl cyanide=1: 16～18 adds vinyl cyanide.Vinyl cyanide adding mode is that the mixing liquid temperature after sodium hydroxide solution and reaction solvent are stirred splashes into when being down to below 40 ℃, and miscible with its stirring again under normal temperature condition, churning time is no less than 30min.
The present invention adopts a step isothermal reaction method, and initial reaction temperature is 45 ℃, and under this constant temperature, optimum reacting time is 4～5h.Maximum temperature is 70 ℃, and under this constant temperature, optimum reacting time is 2～2.5h.Both select one.Reaction temperature is spent low or too high, all can influence the replacement degree of product.Reaction times, long meeting produced a large amount of impurity, influenced the yield of product.Key is to control temperature constant state well, and the temperature difference in the same isothermal reaction process must not surpass 5 ℃ of scopes.This is because the regularity of the molecular arrangement of fibre-grade polyvinyl alcohol determines.At last with in the acetic acid and termination reaction.
For guaranteeing substitution value and the purity of product, the present invention has adopted two one-step refining methods.At first, behind the reaction terminating, adopt the mode of decomposition and distillation, remove residual organic reaction solvent and impurity.Method is successively to add concentration to be all 35% ethanolic soln and acetone soln dilution residual process solvent, carries the evolution reaction product, distills out the impurity that produces in remaining mixed solvent and the reaction process with the method gradation of distilling, and distillation temperature is not higher than 95 ℃.
Take first high-temperature digestion again, the mode that back cold water leaves standstill is removed unsubstituted hydroxyl and other impurity in the reactant, and method is that the product behind the removal residual solvent is placed 70 ℃～90 ℃ water agitator treatings, separate out with acetone solution again after the cooling, the deionized water repetitive scrubbing, leave standstill.Remove moisture to constant weight finally by vacuum drying.
The present invention is directed to the feature of raw material, early stage raw material has been carried out the water dissolution processing in building-up reactions, and found the cosolvent of polyvinyl alcohol solution and vinyl cyanide and reacted process solvent, destroyed hydrogen bond structure, improved etherificate efficient, building-up reactions is carried out in fused solution and homogeneous system all the time simultaneously, and more fully with even, the substitution value of product and purity, dielectric properties have obtained guarantee in etherification modified reaction.
Embodiment
Embodiment 1
The four-hole boiling flask that agitator and thermometer, reflux condensing tube are housed is positioned in the constant temperature waters.Be 2400 toward the interior adding of the bottle 4g polymerization degree successively, the polyvinyl alcohol of alcoholysis degree 98% (mole%) (the Japanese Kuraray PVA-124 of company) and 20ml water, 90 ℃～95 ℃ stirrings heat up, all dissolve until polyvinyl alcohol, be cooled to 40 ℃, add the 40ml dimethyl sulfoxide (DMSO), heat up 90 ℃ again, it is bright until the liquid full impregnated to stir 30min, be cooled to 40 ℃, with 10% sodium hydroxide solution of 3ml at the uniform velocity splash into stir in the bottle after, add 80ml vinyl cyanide stirring at normal temperature 40min, 45 ℃ of constant temperature stirring reaction 4～5h heat up, splash in the acetum and termination reaction, record PH≤7, adding an amount of concentration is 35% ethanolic soln, and stirring heats up distills out residual mixed solvent, distillation temperature is not higher than 95 ℃, be cooled to 50 ℃, add an amount of concentration again and be 35% acetone soln, stirring heats up distills out residual mixed solvent, till reactant is all separated out, remaining liq in the sucking-off flask adds deionized water agitator treating in 70 ℃ of water of temperature, is cooled to room temperature, reactant poured in the beaker that fills acetone and separate out after the dissolving, use the deionized water repetitive scrubbing again, left standstill 5 days, draining send in the vacuum drying oven oven dry to remove in the reactant moisture to constant weight.
Embodiment 2
The four-hole boiling flask that agitator and thermometer, reflux condensing tube are housed is positioned in the constant temperature waters.Be 3500 toward the interior adding of the bottle 4g polymerization degree successively, the polyvinyl alcohol of alcoholysis degree 99% (mole%) (the Japanese Kuraray PVA-135 of company) and 25ml distilled water, 90 ℃～95 ℃ stirrings heat up, all dissolve until polyvinyl alcohol, be cooled to 40 ℃, add the 55ml dimethyl sulfoxide (DMSO), heat up 90 ℃ again, stir 40min until the miscible transparent liquid of helping, be cooled to 40 ℃, with 10% sodium hydroxide solution of 2.5ml at the uniform velocity splash into stir in the bottle after, add 95ml vinyl cyanide stirring at normal temperature 40min, 70 ℃ of constant temperature stirring reaction 2～2.5h heat up, splash in the acetic acid and termination reaction, record PH≤7, adding an amount of concentration is 35% ethanolic soln, stirring heats up distills out residual mixed solvent, distillation temperature is not higher than 95 ℃, be cooled to 50 ℃, add an amount of concentration again and be 35% acetone soln, stirring heats up distills out residual mixed solvent, till reactant is all separated out, remaining liq in the sucking-off flask adds deionized water agitator treating in 70 ℃～90 ℃ water of temperature, is cooled to room temperature, reactant poured in the beaker that fills acetone and separate out after the dissolving, use the deionized water repetitive scrubbing again, left standstill 5 days, draining send in the vacuum drying oven oven dry to remove in the reactant moisture to constant weight.
Claims (10)
1. modification synthetic method that possesses the high viscosity film-forming resin of dielectricity, be that the selective polymerization degree is 2400～3500, the fibre-grade polyvinyl alcohol is as raw material, earlier with miscible with dimethyl sulfoxide (DMSO) by a certain percentage after the polyvinyl alcohol water dissolution, after its temperature is down to below 40 ℃, add 10% sodium hydroxide solution account for polyvinyl alcohol quality 6%～9% and a certain proportion of vinyl cyanide again and under 45 ℃ or 70 ℃ of constant temperatures, polyvinyl alcohol is carried out homogeneous phase etherification reaction 2～5h, obtain the cyanoethyl etherate.
2. synthetic method according to claim 1, the polyvinyl alcohol of it is characterized in that between the selective polymerization degree 2400～3500, alcoholysis degree 98mol% is above is for best.
3. synthetic method according to claim 1 is characterized in that polyvinyl alcohol solution optimal dissolution degree is 15%～20%.
4. synthetic method according to claim 1 is characterized in that the miscible best volumetric ratio of polyvinyl alcohol solution and dimethyl sulfoxide solvent is polyvinyl alcohol solution: dimethyl sulfoxide solvent=1: 2～3.
5. synthetic method according to claim 1, the miscible method that it is characterized in that polyvinyl alcohol solution and dimethyl sulfoxide solvent is to mix under 90 ℃ of constant temperatures, the period is at 30～50min.
6. synthetic method according to claim 1 is characterized in that sodium hydroxide solution adding mode is to splash into when being down to the temperature of polyvinyl alcohol solution and dimethyl sulfoxide (DMSO) mixing liquid below 40 ℃.
7. synthetic method according to claim 1, the add-on that it is characterized in that vinyl cyanide are by polyvinyl alcohol: the mass ratio of vinyl cyanide=1: 16～18.
8. synthetic method according to claim 1 is characterized in that vinyl cyanide adding mode is that mixing liquid temperature after sodium hydroxide solution and polyvinyl alcohol solution and dimethyl sulfoxide (DMSO) are stirred splashes into when being down to below 40 ℃.
9. synthetic method according to claim 8 is characterized in that vinyl cyanide need stir misciblely with the mixing solutions that adds polyvinyl alcohol solution behind the sodium hydroxide and dimethyl sulfoxide (DMSO) under normal temperature condition, the miscible time of normal temperature is no less than 30min.
10. synthetic method according to claim 1 is characterized in that adopting a step constant temperature synthetic method, and under 45 ℃ or 70 ℃ of constant temperatures, corresponding reaction times control is at 4～5h or 2～2.5h, and both select one.
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| CN102942645B (en) * | 2012-10-22 | 2014-09-24 | 广州市杰迅电子材料有限公司 | Preparation method and application of modified polyvinyl alcohol resin |
| CN105153336B (en) * | 2015-10-14 | 2017-12-08 | 天津一森材料科技有限公司 | A kind of polyvinyl acetate cyanoethyl etherate and its synthetic method |
| CN115889369B (en) * | 2023-02-24 | 2023-07-18 | 山西钢科碳材料有限公司 | Method for cleaning gel of acrylonitrile polymerization reaction kettle |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1528799A (en) * | 2003-09-27 | 2004-09-15 | 无锡市化工研究设计院宜兴联营实验厂 | Improved polyvinyl alcohol-beta-cyanoethyl ether preparing method |
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| JP2006114372A (en) * | 2004-10-15 | 2006-04-27 | Mitsubishi Gas Chem Co Inc | Solid polymer electrolyte and solid polymer electrolyte membrane |
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| CN1528799A (en) * | 2003-09-27 | 2004-09-15 | 无锡市化工研究设计院宜兴联营实验厂 | Improved polyvinyl alcohol-beta-cyanoethyl ether preparing method |
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