CN1040800A - The manufacture method of polyvinyl acetal resin - Google Patents
The manufacture method of polyvinyl acetal resin Download PDFInfo
- Publication number
- CN1040800A CN1040800A CN 88105329 CN88105329A CN1040800A CN 1040800 A CN1040800 A CN 1040800A CN 88105329 CN88105329 CN 88105329 CN 88105329 A CN88105329 A CN 88105329A CN 1040800 A CN1040800 A CN 1040800A
- Authority
- CN
- China
- Prior art keywords
- polyvinylacetal
- manufacture method
- polyvinyl alcohol
- acid
- acetaldehyde
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/28—Condensation with aldehydes or ketones
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A kind of manufacture method of polyvinylacetal.Aldolization takes place in main polyvinyl alcohol and the acetaldehyde of adopting under the condition that has acid to exist.Polyvinyl alcohol is 70-85 part, and acetaldehyde is 20-80 part, and acid is 9-30 part.Reaction finishes, and through neutralization, stability is handled.After air stream drying promptly can be made into qualified polyvinyl acetal resin.Manufacture method of the present invention reduces by three road master operations than the homogeneous phase method of prior art.Owing to do not adopt butanols as solvent, can also save a large amount of butanols, therefore, cost is also lower.
Description
The present invention relates to the manufacture method of polyvinyl acetal resin, especially make the method for polyvinylacetal with the different phase method of polyvinyl alcohol and acetaldehyde.
Prior art is to adopt homogeneous phase to make polyvinyl acetal resin, promptly uses Vinyl Acetate Monomer (liquid), through after the polymerization, has sulfuric acid to do under the condition of catalyzer alcoholysis reaction to take place in the butanols solvent.Add acetaldehyde then, under the vitriolic katalysis, carry out acetalation.After filtration, promptly make polyvinylacetal after the neutralization, separation, drying, and to remainder contain that butanols liquid distills, rectifying, recovery butanols.The resin of making is mainly used in modifying plastics, makes paint, wear-resisting disc etc., and the advantage of homogeneous phase method is that the acetalation degree is higher.But the boiling point of vinyl acetate between to for plastic liquid is lower, about about 10 ℃, is difficult for transportation.And transportation equipment and production unit there is the intensive corrosive nature.And have an appointment when the reclaiming butanols of 15-20% of butanols has lost.
The objective of the invention is to adopt different phase method to make polyvinyl acetal resin, promptly carry out acetalation under the condition of catalyzer there being acid to do with the ethanol of solid polyethylene alcohol and liquid.Make polyvinyl acetal resin.
Advantage of the present invention is to use the solid polyvinyl alcohol as main raw material, and convenient transportation does not have corrosion, and technology is simpler, and cost is also lower.
The objective of the invention is to reach like this, solid (granular or cotton-shaped) polyvinyl alcohol is dissolved in hot water becomes the aqueous solution.Having acid to do under the condition of catalyzer, with acetaldehyde generation acetalation, after reaction reached balance, with the alkali lye neutralization, through separating, stability was handled, and drying promptly can be made into polyvinyl acetal resin.
Below the manufacture method of polyvinyl acetal resin of the present invention is explained in detail.
Polyvinyl alcohol with certain polymerization degree and alcoholysis degree, the polymerization degree are between 1700-2400, and alcoholysis degree is greater than 99%, and acetaldehyde, acid and alkali react in order.
Polyvinyl alcohol is put into the reactor with intensification, insulation and whipping device that 50-150 ℃ of hot water is housed carry out stirring in 1-5 hour, fully dissolve, become polyvinyl alcohol water solution with water.In the aqueous solution, add acetaldehyde and catalyst acid, generally use sulfuric acid, nitric acid, hydrochloric acid, preferably use hydrochloric acid, temperature in the reactor remains on 10-25 ℃, through 1-3 hour insulated and stirred, acetalation took place in polyvinyl alcohol and acetaldehyde under the katalysis of acid.Make the polyvinylacetal aaerosol solution.The solution of making is carried out filtering separation with the rotary drum filtration device.The polyvinylacetal that filters to isolate is adsorbed on its lip-deep acid with the alkali lye neutralization.Alkali can use caustic soda, soda ash or potassium hydroxide.Treat that solution reaches neutral (PH7-8), add stablizer, general organic amine or the Resorcinol of using, preferably use Resorcinol, the stability of carrying out 2-3 hour is handled, and dries with centrigugal swing dryer then, dry the back and in drying tower, use 90-150 ℃ hot gas flow, adopt and the fluidized drying method, with the polyvinylacetal thorough drying, the outward appearance that can obtain degree of acetalization and be 30-80% uniformly white to micro-yellow powder shaped polyethylene alcohol acetate resin.
The homogeneous phase method: vinyl acetate between to for plastic and butanols and acetaldehyde are the reaction of liquid.Be called the homogeneous phase method.
Different phase method: polyvinyl alcohol is a solid, and acetaldehyde is liquid, and solid-liquid reaction is called different phase method.
In the different phase method of the present invention, the formula rate of each component is as follows: (weight ratio)
Polyvinyl alcohol (solid) 70-85 part, acetaldehyde 20-80 part, acid (catalyzer) 9-30 part, alkali is till neutralization.Resorcinol (stablizer).
Provide the specific embodiment of the manufacture method of polyvinyl acetal resin of the present invention below.
Raw material:
The polymerization degree is the polyvinyl alcohol of 1700-2400; Industrial acetaldehyde.
Catalyzer:
General industry is with hydrochloric acid or sulfuric acid and soda ash or caustic soda.
Stablizer:
Organic amine or Resorcinol.
Major equipment:
Reactor with intensification, cooling and whipping device, rotary drum filtration device, centrigugal swing dryer, air stream drying tower etc.
Embodiment 1:
70 parts of polyvinyl alcohol are put into the reactor that 50-150 ℃ of hot water is housed, insulated and stirred through 1-5 hour, after treating that polyvinyl alcohol fully is dissolved in water, add 20 parts of acetaldehyde, add 9 parts of hydrochloric acid (or sulfuric acid) simultaneously, reactor temperature is controlled at 10-25 ℃, start stirrer, insulated and stirred 1-3 hour, behind the molecular balance, solution is filtered by the rotary drum filtration device, separate.After the separation, add in the soda ash liquid (or caustic soda), neutralization is adsorbed on the acid on polyvinylacetal surface.When solution is neutral (PH7-8), in solution, add stablizer organic amine or Resorcinol, preferably use Resorcinol.Handle through 2-3 hour stability, solution is inserted in the centrigugal swing dryer, moisture content is dried.Be preferably in and use 90-150 ℃ hot gas flow in the drying tower, adopt also and flow the polyvinyl alcohol thorough drying.Can obtain degree of acetalization and be 30% outward appearance uniformly white to micro-yellow powder shaped polyethylene alcohol acetate resin.
Embodiment 2:
80 parts of polyvinyl alcohol are put into the reactor that 50-150 ℃ of hot water is housed, insulated and stirred through 1-5 hour, after treating that polyvinyl alcohol fully is dissolved in water, add 40 parts of acetaldehyde, add 15 parts of hydrochloric acid (or sulfuric acid) simultaneously, reactor temperature is controlled at 10-25 ℃, start stirrer, insulated and stirred 1-3 hour, behind the molecular balance, solution by the rotary drum filtration device, is separated.After the separation, add in the soda ash liquid (or caustic soda), neutralization is adsorbed on the acid on polyvinylacetal surface, when solution is neutral (PH7-8), in solution, add stablizer organic amine or Resorcinol, handle through 2-3 hour stability, solution is inserted in the centrigugal swing dryer, moisture content is dried.The last hot gas flow of using 90-150 ℃ in drying tower adopts cocurrent process with the polyvinylacetal thorough drying.Can obtain degree of acetalization and be 50% outward appearance uniformly white to little yellow powder polyvinyl acetal resin.
Embodiment 3:
85 parts of polyvinyl alcohol are put into the reactor that 50-150 ℃ of hot water is housed, insulated and stirred through 1-5 hour, after treating that polyvinyl alcohol fully is dissolved in water, add 80 parts of acetaldehyde, add 30 parts of hydrochloric acid (or sulfuric acid) simultaneously, reactor temperature is controlled at 10-25 ℃, start stirrer, insulated and stirred 1-3 hour, behind the molecular balance, solution is filtered by the rotary drum filtration device, separate.Separate the back and add in the soda ash liquid (or caustic soda), neutralization is adsorbed on the acid on polyvinylacetal surface.When solution is neutral (PH7-8), in solution, add stablizer organic amine or Resorcinol, preferably adopt Resorcinol, handle through 2-3 hour stability, solution is inserted in the centrigugal swing dryer, moisture content is dried.The last hot gas flow of using 90-150 ℃ in drying tower adopts cocurrent process with the polyvinylacetal thorough drying.Can obtain degree of acetalization and be 80% outward appearance uniformly white to micro-yellow powder shaped polyethylene alcohol acetate resin.
Below the homogeneous phase method of prior art and the master operation of different phase method of the present invention are compared explanation:
Operation prior art the technology of the present invention remarks
The dissolving of 1 vinyl acetate polymerization polyvinyl alcohol
2 are dissolved in (acid adding) and acetaldehyde reaction (acid adding) in the butanols
3 with acetaldehyde reaction (acid adding) isolated by filtration
4 isolated by filtration neutralizations (adding alkali)
5 neutralization (adding alkali) disposal of stabilities
6 disposal of stability centrifuge drippings
7 centrifuge dripping dryings
8 dryings
Butanols is reclaimed in 9 distillations
Butanols is reclaimed in 10 rectifying
As can be seen from the above table, the manufacture method of polyvinyl acetal resin of the present invention reduces by three road master operations than prior art, and therefore, technology, equipment are all simpler, and cost is lower.
Claims (10)
1, a kind of manufacture method of polyvinylacetal, it is characterized in that the solid polyvinyl alcohol through the aqueous solution after the water dissolution and liquid acetaldehyde solution jointly under the condition that acid catalyst exists, in the reactor that heating and cooling insulation and whipping device are arranged, carry out acetalation, pass through the filter filtering separation afterwards, the alkali lye neutralization, the stability of stablizer is handled, centrifuge dripping and hot gas flow drying.
2,, it is characterized in that the consumption (weight ratio) of said each reactive material and catalyzer and alkali lye is as described below according to the manufacture method of the described polyvinylacetal of claim 1.
Polyvinyl alcohol 70-85
Acetaldehyde 20-80
Acid 9-30
Alkali to acid all is neutralized to PH7-8.
3, according to the manufacture method of the described polyvinylacetal of claim 1, it is characterized in that the temperature of the water of said dissolve polyvinyl alcohol is 50-150 ℃, be 1-5 hour during dissolving.
4, according to the manufacture method of the described polyvinylacetal of claim 1, it is characterized in that said polyvinyl alcohol and the acetaldehyde temperature of reaction in reactor is 10-25 ℃, the stirring reaction time is 1-5 hour.
5,, it is characterized in that said acid catalyst is a hydrochloric acid according to the manufacture method of the described polyvinylacetal of claim 1.
6, according to the manufacture method of the described polyvinylacetal of claim 1, it is characterized in that being used for neutral alkali is soda ash.
7,, it is characterized in that said stablizer is organic amine or Resorcinol according to the manufacture method of the described polyvinylacetal of claim 1.
8,, it is characterized in that said air stream drying is with 90-150 ℃ the overfire air stream also airflow flowing drying identical with the flow direction of polyvinylacetal in drying tower according to the manufacture method of the described polyvinylacetal of claim 1.
9, according to the manufacture method of the described polyvinylacetal of claim 1, the polymerization degree that it is characterized in that said polyvinyl alcohol is 1700-2400.Alcoholysis degree is 98-99.5%.
10, according to the manufacture method of the described polyvinylacetal of claim 1, the degree of acetalization that it is characterized in that said polyvinylacetal is 30-80.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105329 CN1040800A (en) | 1988-08-26 | 1988-08-26 | The manufacture method of polyvinyl acetal resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88105329 CN1040800A (en) | 1988-08-26 | 1988-08-26 | The manufacture method of polyvinyl acetal resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1040800A true CN1040800A (en) | 1990-03-28 |
Family
ID=4833535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88105329 Pending CN1040800A (en) | 1988-08-26 | 1988-08-26 | The manufacture method of polyvinyl acetal resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1040800A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101454354B (en) * | 2006-06-01 | 2013-08-21 | 可乐丽欧洲有限责任公司 | Highly acetalized coarse granular polyvinyl acetal |
| CN105504117A (en) * | 2016-02-01 | 2016-04-20 | 营口天元化工研究所股份有限公司 | Preparation method of high-tenacity low-water absorbability carbon-oxygen-crosslinked polyvinyl acetal insulating material |
-
1988
- 1988-08-26 CN CN 88105329 patent/CN1040800A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101454354B (en) * | 2006-06-01 | 2013-08-21 | 可乐丽欧洲有限责任公司 | Highly acetalized coarse granular polyvinyl acetal |
| CN105504117A (en) * | 2016-02-01 | 2016-04-20 | 营口天元化工研究所股份有限公司 | Preparation method of high-tenacity low-water absorbability carbon-oxygen-crosslinked polyvinyl acetal insulating material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2091128C (en) | Removal of organic volatiles from polymer solutions and dispersions | |
| WO2001032597A1 (en) | Method of purifying bishydroxyalkyl terephthalate | |
| CN102020735B (en) | Purification method of polyvinyl alcohol | |
| KR20140106749A (en) | Process technology for recovering brominated styrenic polymers from reaction mixtures in which they are formed and/or converting such mixtures into pellets or into granules or pastilles | |
| CN1481413A (en) | Ways to deal with mixed plastic waste | |
| CN1265640A (en) | Purification method of (meth)acrylic acid | |
| CN86108257A (en) | Handle the method for ethene/carbon monoxide multipolymer | |
| WO1996031494A1 (en) | Method to produce and purify cyclic esters | |
| RU2036201C1 (en) | Method of preparing catalyst for copolymerization of ethylene with butene-1 | |
| CN101056922B (en) | Method for purifying a solution containing a plastic material | |
| CN1040800A (en) | The manufacture method of polyvinyl acetal resin | |
| CN101243124B (en) | Process for recovering polymers from liquid media | |
| CA1204371A (en) | Washing and removal method of high molecular substances and recovery method of washing solvent | |
| CN100532399C (en) | Extraction of Impurities from Grafted Polyolefins | |
| EP0374879B1 (en) | Method for extraction of impurities in polymer | |
| CN111100240B (en) | System and method for preparing maleic anhydride copolymer microspheres | |
| CA2040949A1 (en) | Removal of residual acid from chlorinated polymers | |
| CA1050979A (en) | Process for purifying cyanuric acid | |
| US2534079A (en) | Granular polymers and process for their preparation | |
| CN115991802A (en) | A kind of production method of low methanol polyvinyl alcohol | |
| CN100584825C (en) | Method for preparing solid three (2,3-dibromopropyl) isocyanurate | |
| SE453919B (en) | SET FOR PREPARATION OF POWDER-HOMO OR COPOLYMERS OF ONE | |
| CN111100239B (en) | System and method for preparing crosslinked maleate ionomer microspheres | |
| Zhou et al. | The Polyurethane/5A Zeolite Hybrid Hydrogel with Thermal-and pH-Sensitivity for Removing Acid Fuchsin from Aqueous Solutions | |
| CN116199835B (en) | A method for separating and purifying electronic grade pyridine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |