CN103739749A - Polyvinyl formal resin and production method thereof - Google Patents
Polyvinyl formal resin and production method thereof Download PDFInfo
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- CN103739749A CN103739749A CN201310644831.8A CN201310644831A CN103739749A CN 103739749 A CN103739749 A CN 103739749A CN 201310644831 A CN201310644831 A CN 201310644831A CN 103739749 A CN103739749 A CN 103739749A
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- acetic acid
- pva
- formal resin
- sulfuric acid
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Abstract
The invention provides a polyvinyl formal resin and a production method thereof, wherein the raw materials comprise PVA, deionized water, glacial acetic acid, a formaldehyde aqueous solution (37%) and sulfuric acid (30%). The production method comprises: dissolving polyvinyl alcohol (PVA) in deionized water, adding glacial acetic acid, a formaldehyde aqueous solution and sulfuric acid (catalyst) to carry out a reaction to produce a polyvinyl formal solution, and directly carrying out spray drying to obtain the finely-granular acetalation finished product, wherein the solvent vapor enters a condenser so as to be collected, and rectification recovery is performed to use the acetic acid. According to the present invention, with application of the method to produce the polyvinyl formal resin, repeated utilization of the acetic acid solvent can be achieved so as to save the resource; the finished product with finely-granular acetalization of greater than 75% is directly obtained through spray drying so as to simplify the process and the equipment and improve the production efficiency; and less harmful substances are generated during the production process so as to reduce the environmental pollution.
Description
Technical field
The invention belongs to chemical field, especially relate to a kind of production method of vinyl-formal resin.
Background technology
In existing technology, it is to carry out solution polymerization by vinyl acetate that traditional polyvinyl alcohol formal (PVF) is produced, and obtains polyvinyl acetate (PVA); Pass through again alcoholysis, acetalation (its alcoholysis, acetalation are that synchronous reaction completes), by separating out, wash, drying, obtain finished product.The not reproducible utilization of solvent after this production method is not only used, has wasted resource, and the material producing in production process, is not well processed, and environmental pollution degree is larger.
Summary of the invention
The object of this invention is to provide a kind of production method of vinyl-formal resin, can realize the recycling of acetate solvate, saved resource, simplify Processes and apparatus, reduced the pollution to environment.
Technical scheme of the present invention is: a kind of production method of vinyl-formal resin, by soluble in water polyvinyl alcohol (PVA), adds acetic acid, formaldehyde, sulfuric acid (catalyzer) reaction to generate polyvinyl formal solution; The spray-dried fine particulate acetalation finished product that directly obtains; Specifically carry out as follows:
1. batching is as follows: (by weight percentage) PVA: 15～25%, and deionized water: 22.5～32.5%, Glacial acetic acid: 19.5～35.5%, formalin (37%): 15～25%, sulfuric acid (30%): 4～6%.
Further, described formula is take following as best: PVA:20%, and deionized water: 27.5%, Glacial acetic acid: 27.5%, formalin (37%): 20%, sulfuric acid (30%): 5%.
2. technological process
(1) deionized water is dropped into reactor and stir (300 revs/min), drop into PVA simultaneously, heating 90-100 ℃, dissolves 2-3 hour, and it is all dissolved.
After dissolving, be cooled to below 40 ℃, drop into Glacial acetic acid, formalin, stir 1-2 hour, evenly rear 30% sulfuric acid (as catalyzer) that drops into, is heated to 85 ℃, reacts 20 hours, is cooled to 50 ℃ after finishing.
(2) solution sprays in spray-dryer by nozzle, and spray-dryer internal temperature is controlled at 150～200 ℃, from bottom collecting granules shape finished product.
(3) solvent vapo(u)r enters condenser collection, through rectifying, is reclaiming and is using acetic acid.
Further, in the step of technological process (1), the best temperature of reacting by heating still is: 85 ℃.
Further, in the step of technological process (2), the optimum temps of spray-dryer internal temperature control is: 180 ℃.
Advantage and positively effect that the present invention has are: adopt this method to produce vinyl-formal resin, can realize the recycling of acetate solvate, saved resource; Simplify Processes and apparatus, improved production efficiency; In production process, produce less objectionable impurities, reduced the pollution to environment.
Embodiment
Technical scheme of the present invention is: present method, by soluble in water polyvinyl alcohol (PVA), adds acetic acid, formaldehyde, sulfuric acid (catalyzer) reaction to generate polyvinyl formal solution; Spray-driedly directly obtain the finished product that fine particulate acetalation is greater than 75%, specifically carry out as follows:
1. batching is as follows: (by weight percentage) PVA: 15～25%, and deionized water: 22.5～32.5%, Glacial acetic acid: 19.5～35.5%, formalin (37%): 15～25%, sulfuric acid (30%): 4～6%.
2. instrument and material
Reactor; Stirring rod; Spray-dryer; Condenser.
3. embodiment 1:
27.5% deionized water is dropped into reactor and stir (300 revs/min), drop into 20%PVA simultaneously, heating 90-100 ℃, dissolves 2-3 hour, and it is all dissolved; After dissolving, be cooled to below 40 ℃, drop into 27.5% Glacial acetic acid, 20% formalin, stir 1-2 hour, evenly rear 5% catalyzer (30% sulfuric acid) that drops into, is heated to 85 ℃, reacts 20 hours, is cooled to 50 ℃ after finishing; Solution sprays in spray-dryer by nozzle, and spray-dryer internal temperature is controlled at 150～200 ℃, from bottom collecting granules shape finished product; Solvent vapo(u)r enters condenser and collects, and through rectifying, is reclaiming and is using acetic acid.
Detected result:
Hydroxyl: 5.98% acetoxyl group: 10.08% acetal radical: 83.94% free acid: 0.032% moisture content: 1.36%
Embodiment 2:
26.5% deionized water is dropped into reactor and stir (300 revs/min), drop into 23%PVA simultaneously, heating 90-100 ℃, dissolves 2-3 hour, and it is all dissolved; After dissolving, be cooled to below 40 ℃, drop into 29.5% Glacial acetic acid, 15.5% formalin, stir 1-2 hour, evenly rear 5.5% catalyzer (30% sulfuric acid) that drops into, is heated to 85 ℃, reacts 20 hours, is cooled to 50 ℃ after finishing; Solution sprays in spray-dryer by nozzle, and spray-dryer internal temperature is controlled at 150～200 ℃, from bottom collecting granules shape finished product; Solvent vapo(u)r enters condenser and collects, and through rectifying, is reclaiming and is using acetic acid.
Detected result:
Hydroxyl: 5.87% acetoxyl group: 9.76% acetal radical: 84.37% free acid: 0.04% moisture content: 1.07%
4. the method for inspection
(1) hydroxyl detects:
Weighing polyvinyl alcohol formal dry sample, be placed in iodine flask, add acetic anhydride-pyridine solution with transfer pipet, jump a queue to be placed in boiling water-bath and heat, after heating, after cooling, take off, add 1,2-ethylene dichloride, after mixing, add distilled water, after shaking up, add instructions phenolphthalein solution, with Standard Volumetric Solutions for Sodium Hydroxide, be titrated to solution and become rose pinkly for terminal from colourless, with acetic anhydride-pyridine solution, do blank test calculation result simultaneously.
(2) acetoxyl group detects:
Weighing polyvinyl alcohol formal dry sample, be placed in ground triangular flask, add benzene-ethanol mixture solvent, shake, ground reflux exchanger is installed, reflux on boiling water bath, sample is dissolved completely, after cooling, take off, add instructions phenolphthalein solution, with sodium hydroxide solution, be neutralized to rose pink, add potassium hydroxide-ethanol solution with transfer pipet, again connect ground reflux exchanger, reflux on boiling water bath, after slightly cold, take off, add again instructions phenolphthalein solution, the redness that is titrated to solution with Hydrochloric Standard Titration is decorporated just, with benzene-ethanol mixture solvent, carry out blank test calculation result simultaneously.
(3) acetal radical detects:
Take polyvinylformal sample, be placed in flat long-neck distilling flask, add sulphuric acid soln, install and carry out wet distillation, use volumetric flask to collect and slip out liquid, shake up.Accurately measure distillate, put into clean dry iodine flask, add sodium hydroxide solution, add iodine solution with drop-burette, add sulphuric acid soln, shake up, with Sulfothiorine standard titration solution, be titrated to light yellow, add starch indicating liquid, continue to be titrated to solution and become colorless as terminal by blueness, with the distilled water boiling, do blank test calculation result simultaneously.
(4) free acid detects:
Take and dry rear polyvinyl formal dry sample, be placed in Erlenmeyer flask, add benzene-ethanol mixture solvent, add plug, in water-bath, shake, sample is dissolved completely, with Standard Volumetric Solutions for Sodium Hydroxide, being titrated to solution, from yellow, to become green be terminal calculation result.
(5) water content detection:
Take sample and be placed in the glass culture dish of weighing, put into baking oven and be baked to weight, take out and in moisture eliminator, be cooled to room temperature, weigh and compare calculation result.
Nippon Standard: hydroxyl 5.0-6.5% acetoxyl group 9.5-13% acetal radical >=81% free acid≤0.1% moisture content≤2.2%.
Above one embodiment of the present of invention are had been described in detail, but described content is only preferred embodiment of the present invention, can not be considered to for limiting practical range of the present invention.All equalization variations of doing according to the present patent application scope and improvement etc., within all should still belonging to patent covering scope of the present invention.
Claims (5)
1. vinyl-formal resin, it is characterized in that: prepare burden as follows: (by weight percentage) PVA: 15～25%, deionized water: 22.5～32.5%, Glacial acetic acid: 19.5～35.5%, formalin (37%): 15～25%, sulfuric acid (30%): 4～6%.
2. vinyl-formal resin according to claim 1, it is characterized in that: described formula is take following as best: PVA:20%, deionized water: 27.5%, Glacial acetic acid: 27.5%, formalin (37%): 20%, sulfuric acid (30%): 5%.
3. for the manufacture of a method for vinyl-formal resin claimed in claim 1, it is characterized in that: by soluble in water polyvinyl alcohol (PVA), add acetic acid, formaldehyde, sulfuric acid (catalyzer) reaction to generate polyvinyl formal solution; The spray-dried fine particulate acetalation finished product that directly obtains; Specific embodiment is as follows:
(1) deionized water is dropped into reactor and stir (300 revs/min), drop into PVA simultaneously, heating 90-100 ℃, dissolves 2-3 hour, and it is all dissolved; After dissolving, be cooled to below 40 ℃, drop into Glacial acetic acid, formalin, stir 1-2 hour, evenly rear 30% sulfuric acid (as catalyzer) that drops into, is heated to 85 ℃, reacts 20 hours, is cooled to 50 ℃ after finishing;
(2) solution sprays in spray-dryer by nozzle, and spray-dryer internal temperature is controlled at 150～200 ℃, from bottom collecting granules shape finished product;
(3) solvent vapo(u)r enters condenser collection, through rectifying, is reclaiming and is using acetic acid.
4. a kind of method for the manufacture of vinyl-formal resin according to claim 3, is characterized in that: in the step (1) of technological process, the best temperature of reacting by heating still is: 85 ℃.
5. a kind of method for the manufacture of vinyl-formal resin according to claim 3, is characterized in that: in the step (2) of technological process, the optimum temps of spray-dryer internal temperature control is: 180 ℃.
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| CN201310644831.8A CN103739749A (en) | 2013-12-05 | 2013-12-05 | Polyvinyl formal resin and production method thereof |
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| CN201310644831.8A CN103739749A (en) | 2013-12-05 | 2013-12-05 | Polyvinyl formal resin and production method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312112A (en) * | 2016-08-23 | 2017-11-03 | 如皋长江科技产业有限公司 | A kind of formaldehyde polyvinyl acetal preparation technology |
| CN109679604A (en) * | 2019-01-28 | 2019-04-26 | 中国石油大学(华东) | A kind of salt tolerant high-temperature resistant water gel and the preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319635A (en) * | 2013-06-26 | 2013-09-25 | 四川东材科技集团股份有限公司 | Preparation method of polyvinyl acetal resin |
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2013
- 2013-12-05 CN CN201310644831.8A patent/CN103739749A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103319635A (en) * | 2013-06-26 | 2013-09-25 | 四川东材科技集团股份有限公司 | Preparation method of polyvinyl acetal resin |
Non-Patent Citations (1)
| Title |
|---|
| 柯丽军 等: "聚乙烯醇缩甲醛的研制", 《贵州化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312112A (en) * | 2016-08-23 | 2017-11-03 | 如皋长江科技产业有限公司 | A kind of formaldehyde polyvinyl acetal preparation technology |
| CN109679604A (en) * | 2019-01-28 | 2019-04-26 | 中国石油大学(华东) | A kind of salt tolerant high-temperature resistant water gel and the preparation method and application thereof |
| CN109679604B (en) * | 2019-01-28 | 2021-01-05 | 中国石油大学(华东) | Salt-resistant and high-temperature-resistant hydrogel and preparation method and application thereof |
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Application publication date: 20140423 |