CN103012633A - Preparation method of high-acetalization-degree high-flowability polyvinyl butyral resin - Google Patents
Preparation method of high-acetalization-degree high-flowability polyvinyl butyral resin Download PDFInfo
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- CN103012633A CN103012633A CN2012105414860A CN201210541486A CN103012633A CN 103012633 A CN103012633 A CN 103012633A CN 2012105414860 A CN2012105414860 A CN 2012105414860A CN 201210541486 A CN201210541486 A CN 201210541486A CN 103012633 A CN103012633 A CN 103012633A
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- polyvinyl butyral
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 title claims abstract description 50
- 229920005989 resin Polymers 0.000 title claims abstract description 49
- 239000011347 resin Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 36
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 15
- 238000006359 acetalization reaction Methods 0.000 claims abstract description 13
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 10
- 238000006482 condensation reaction Methods 0.000 claims abstract description 8
- 230000018044 dehydration Effects 0.000 claims abstract description 3
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 3
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims description 29
- 238000009413 insulation Methods 0.000 claims description 27
- 239000011541 reaction mixture Substances 0.000 claims description 10
- -1 butyraldehyde-n Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 abstract description 12
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 abstract description 11
- 239000002253 acid Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 4
- 239000003054 catalyst Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007795 chemical reaction product Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000005336 safety glass Substances 0.000 description 4
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N valeric aldehyde Natural products CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 4
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000010189 synthetic method Methods 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Abstract
The invention provides a preparation method of a high-acetalization-degree high-flowability polyvinyl butyral resin, which comprises the following steps: a. condensation reaction: heating polyvinyl alcohol to 95 DEG C, dissolving in water to prepare a 10% solution, cooling the solution to 40-60 DEG C, adding n-butyl aldehyde to carry out reaction, cooling to 20-25 DEG C, adding a catalyst hydrochloric acid to react for 1 hour, sending the mixed reaction solution to a condensation kettle, gradually heating to 35-40 DEG C within 1 hour, keeping the temperature to react for 1 hour, gradually heating to 50-55 DEG C within 1 hour, keeping the temperature to react for 1 hour, and cooling; b. neutralizing treatment: sending the cooled reaction solution to a water washing kettle to carry out water washing 5-6 times, heating to 40-50 DEG C, adding a right amount of caustic soda solution to regulate the pH value to 8-10, and keeping the temperature for 2-3 hours for sufficient neutralization and acid removal; and c. dehydration and drying: washing the reaction solution subjected to neutralization and acid removal with water 6-8 times, and dehydrating and drying with a centrifugal machine to obtain the polyvinyl butyral resin finished product. The polyvinyl butyral resin prepared by the method provided by the invention has the advantages of high acetalization degree and favorable flowability.
Description
Technical field
The invention belongs to red shortness's technical field of polymer materials, relate in particular to the preparation method of high degree of acetalization, high workability polyvinyl butyral resin.
Background technology
Polyvinyl butyral resin has high-performance in the transparency, film-forming properties, winter hardiness, shock resistance, uvioresistant and aspect the cohesiveness of glass, pottery etc.Polyvinyl butyral acetal is the indispensable material of preparation laminated safety glass, along with automobile industry, construction industry, the development of photovoltaic industry, the consumption of laminated safety glass is increasing, China market is increasing to the demand of polyvinyl butyral resin, but domestic do not have producer to supply with, overwhelming majority dependence on import, and mainly by U.S. Meng Shan all, this three major company of Du Pont and Japanese ponding monopolizes, therefore the invention of the synthetic method of this polyvinyl butyral resin, break external technical monopoly, broken through the passive situation of the long-term dependence on import of pvb film.
The synthetic method of China Patent No. 201210161377.6 polyvinyl butyral resins is through low temperature continuous condensating and the polyvinyl butyral resin that again obtains after the condensation reaction take polyvinyl alcohol and butyraldehyde-n as raw material, take hydrochloric acid as catalyzer.In this method, it at first is the low temperature continuous condensating, butyraldehyde-n, the hydrochloric acid of polyvinyl alcohol with an amount of material ratio is begun to react in 0 ℃, then be warming up to gradually 35 ℃ and continue reaction 2 hours, afterwards with the butyraldehyde-n of the resin that generates and leftover materials ratio, mixed in hydrochloric acid in methyl alcohol, in 45-75 ℃ of reaction 4 hours, obtain the polyvinyl butyral resin of degree of acetalization＞78% through aftertreatment.But thereby the 45-75 ℃ of reaction that directly be warming up in this law easily caused the fracture of product macromolecular chain to affect product strength and stability in 4 hours, caused processing the usage quantity that film forming need improve processing temperature or softening agent, and processing difficulties and cost are high.
Summary of the invention
Purpose of the present invention is intended to overcome the shortcoming that above-mentioned prior art exists, the preparation method of a kind of high degree of acetalization, high workability polyvinyl butyral resin is provided, the degree of acetalization of polyvinyl butyral resin that the method prepares gained is high, good fluidity, and production process is simple, need not secondary mixing secondary charging, and work flow is short, need not use inflammable and explosive solvent methanol, safety and environmental protection.
In order to realize the purpose of foregoing invention, the invention provides the preparation method of a kind of high degree of acetalization, high workability polyvinyl butyral resin, the method comprises the steps:
Step 1, condensation reaction:
At first, polyvinyl alcohol is warmed up to 95 ℃ is dissolved in water to be made into concentration be 10% solution, this solution is cooled to 40-60 ℃ add butyraldehyde-n and react;
Secondly, described reaction mixture is cooled to 20-25 ℃, add catalyzer hydrochloric acid, insulation reaction at least 1 hour is delivered to reaction mixture condensation two stills again, is warming up to gradually 35-40 ℃ at 1 hour, insulation reaction is 1 hour again, again be warming up to gradually 50-55 ℃ with 1 hour afterwards, insulation reaction is 1 hour again, then cools to room temperature;
Step 2, neutralizing treatment: described cooled reaction solution is delivered to washing kettle washing 5-6 time, is warming up to afterwards 40-50 ℃, add an amount of caustic soda soln and regulate pH value to 8-10, be incubated again 2-3 hour, fully neutralization deacidification;
Step 3, dehydration, drying: the reaction solution after the described neutralization deacidification is washed 6-8 time again by namely making described polyvinyl butyral resin finished product behind the centrifuge dewatering after water ratio enters the cyclone dryer drying less than 30% with air-flow.
Further, the mass ratio of polyvinyl alcohol, butyraldehyde-n, hydrochloric acid and water is 100:58-60:48-50:900-1000 in the described condensation reaction; The mass concentration of described hydrochloric acid is 30-35%.
The present invention compared with prior art possesses following outstanding substantive distinguishing features and significant progressive:
1) temperature that reaction mass polyvinyl alcohol and butyraldehyde-n mix among the described preparation method is 40-60 ℃, butyraldehyde is in disposable whole input polyvinyl alcohol solution, because butyraldehyde is slightly soluble in water, floating on solution surface behind the lower adding of low temperature (0-10 ℃) polyvinyl alcohol water solution solution disperses irregular, easily cause the local fast response of crossing, formation gel caking, and when polyvinyl alcohol water solution is cooled to 40-60 ℃, add, dispersion effect is good in continuing cooling mixing process, mixing of materials is even, can reduce greatly the resin caking of generation, well improves the degree of uniformity of resin-oatmeal, the product compaction rate is high, can obtain packing density＞2.0g/cm
3Polyvinyl butyral resin.
2) related normal-temperature continuous condensation is compared with the prior art among the described preparation method, after initial reaction temperature is brought up to normal temperature (20-25 ℃) by low temperature (0-10 ℃), speed of response is accelerated, and the polyvinyl alcohol molecule chain easily launches simultaneously, and functional group exposes, activity is high, and the motion of small molecules butyraldehyde is active, condensation reaction easily occurs, and product very easily reaches higher degree of acetalization content, passes through the intensification condensation of multistep again, slaking is stable, very easily obtains the polyvinyl butyral resin of degree of acetalization＞80%.
3) related normal-temperature continuous condensation is compared with the prior art among the described preparation method, after initial reaction temperature is brought up to normal temperature (20-25 ℃) by low temperature (0-10 ℃), can guarantee the expansion that the products molecule chain is larger, the more butyraldehyde group of condensation, can not curl after acetalation is finished under higher temperature, synthetic product butyraldehyde Ji Gengyi exposes, with softening agent better plastification occurs very easily, good fluidity, condensation not only can better prevent resin-bonded under the high temperature than once being raised in continuous several times intensification condensation in addition, and can reduce greatly because the too fast product macromolecular chain that causes that heats up ruptures, have influence on the stability of product.
4) mass ratio of polyvinyl alcohol, butyraldehyde-n, hydrochloric acid and water is that the mass concentration of the employed hydrochloric acid of 100:58-60:48-50:900-1000(is 30-35% in the condensation reaction among the described preparation method), used the catalyzer hydrochloric acid of very high percentage in the prescription, can guarantee concentration and the homogeneity of solution acid in the large-size reactor, guarantee the reactor product homogeneity, be conducive to improve the flowability of polyvinyl butyral resin, can obtain the polyvinyl butyral resin of melting index＞1.5g/10Min after building-up process finishes.
5) process in 40-50 ℃ of lower neutralization after reaction finishes, the polyvinyl butyral resin molecular chain that generates easily launches, stick to the hydrochloric acid small molecules on molecular chain surface very easily by the alkali that is added neutralization, reduced the number of times of product washing, can obtain stable polyvinyl butyral resin.
To sum up, the present invention has improved tap density, degree of acetalization and the flowability of polyvinyl butyral resin, stability to product also improves a lot, and what have also that product that this invention technology makes can be fabulous is applied to automobile industry, construction industry and photovoltaic industry, and profit margin is large.
Can further be well understood to the present invention by specific embodiments of the invention given below.But they are not limitation of the invention.
Embodiment
Embodiment 1
Polyvinyl alcohol 100g is warmed up to 95 ℃ to be dissolved in the 900g water, cool to again the butyraldehyde-n that adds whole ratios to 45 ℃, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to 20 ℃ of temperature of reaction, the hydrochloric acid that adds whole ratios, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, the hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 35 ℃ gradually with 1 hour, insulation reaction 1 hour, again be warming up to gradually 50 ℃ with 1 hour afterwards, then insulation reaction 1 hour washes reaction product 6 times after the cooling down, be warming up to afterwards 45 ℃, add an amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, fully neutralization deacidification, again wash at last 8 times, the polyvinyl butyral resin after the washing makes the polyvinyl butyral resin finished product through centrifugal drying.
Embodiment 2
Polyvinyl alcohol 100g is warmed up to 95 ℃ to be dissolved in the 900g water, cool to again the butyraldehyde-n that adds whole ratios to 45 ℃, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to 25 ℃ of temperature of reaction, the hydrochloric acid that adds whole ratios, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, the hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 40 ℃ gradually with 1 hour, insulation reaction 1 hour, again be warming up to gradually 55 ℃ with 1 hour afterwards, then insulation reaction 1 hour washes reaction product 6 times after the cooling down, be warming up to afterwards 45 ℃, add an amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, fully neutralization deacidification, again wash at last 8 times, the polyvinyl butyral resin after the washing makes the polyvinyl butyral resin finished product through centrifugal drying.
Embodiment 3
Polyvinyl alcohol 100g is warmed up to 95 ℃ to be dissolved in the 900g water, cool to again the butyraldehyde-n that adds whole ratios to 45 ℃, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to 20 ℃ of temperature of reaction, the hydrochloric acid that adds whole ratios, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, the hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 35 ℃ gradually with 1 hour, insulation reaction 1 hour, again be warming up to gradually 50 ℃ with 1 hour afterwards, then insulation reaction 1 hour washes reaction product 6 times after the cooling down, be warming up to afterwards 45 ℃, add a small amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, fully neutralization deacidification, again wash at last 8 times, the polyvinyl butyral resin after the washing makes the polyvinyl butyral resin finished product through centrifugal drying.
Embodiment 4
Polyvinyl alcohol 100g is warmed up to 95 ℃ to be dissolved in the 900g water, cool to again the butyraldehyde-n that adds whole ratios to 45 ℃, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to 25 ℃ of temperature of reaction, the hydrochloric acid that adds whole ratios, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, the hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 40 ℃ gradually with 1 hour, insulation reaction 1 hour, again be warming up to gradually 55 ℃ with 1 hour afterwards, then insulation reaction 1 hour washes reaction product 6 times after the cooling down, be warming up to afterwards 55 ℃, add a small amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, fully neutralization deacidification, again wash at last 8 times, the polyvinyl butyral resin after the washing makes the polyvinyl butyral resin finished product through centrifugal drying.
Comparative example 1
Polyvinyl alcohol 100g is warmed up to 95 ℃ to be dissolved in the 900g water, cool to again the butyraldehyde-n that adds whole ratios to 20 ℃, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, stirring adds the hydrochloric acid of whole ratios after half hour, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, the hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 35 ℃ gradually with 1 hour, insulation reaction 1 hour was warming up to 50 ℃ with 1 hour afterwards again gradually, insulation reaction 1 hour, then after the cooling down reaction product is washed 6 times, be warming up to afterwards 45 ℃, add an amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, fully neutralization deacidification is washed 8 times at last again, and the polyvinyl butyral resin after the washing makes the polyvinyl butyral resin finished product through centrifugal drying.
Comparative example 2
Polyvinyl alcohol 100g is warmed up to 95 ℃ to be dissolved in the 900g water, cool to again the butyraldehyde-n that adds whole ratios to 45 ℃, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to 5 ℃ of temperature of reaction, the hydrochloric acid that adds whole ratios, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, the hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 40 ℃ gradually with 1 hour, insulation reaction 1 hour, again be warming up to gradually 55 ℃ with 1 hour afterwards, then insulation reaction 1 hour washes reaction product 6 times after the cooling down, be warming up to afterwards 45 ℃, add an amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, fully neutralization deacidification, again wash at last 8 times, the polyvinyl butyral resin after the washing makes the polyvinyl butyral resin finished product through centrifugal drying.
Comparative example 3
Polyvinyl alcohol 100g is warmed up to 95 ℃ to be dissolved in the 900g water, cool to again the butyraldehyde-n that adds whole ratios to 45 ℃, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to 20 ℃ of temperature of reaction, the hydrochloric acid that adds whole ratios, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, the hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again with reaction solution with being rapidly heated half an hour to 50 ℃, insulation reaction 2 hours, then after the cooling down with reaction product washing 6 times, be warming up to afterwards 45 ℃, add a small amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, fully neutralization deacidification, again wash at last 8 times, the polyvinyl butyral resin after the washing makes the polyvinyl butyral resin finished product through centrifugal drying.
Comparative example 4
Polyvinyl alcohol 100g is warmed up to 95 ℃ is dissolved in the 900g water, add an amount of hydrochloric acid and butyraldehyde-n, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n: hydrochloric acid=8:4:3, and the hydrochloric acid mass concentration is 32%; Wherein butyraldehyde-n drops at twice, and twice input ratio is 1:1.Its concrete control step is, throws hydrochloric acid and butyraldehyde-n when treating condensation kettle greenhouse cooling to 5 ℃, and question response drops into butyraldehyde-n after 1 hour again, waits and reacts after 1 hour with being warming up to gradually 35 ℃ of again insulation reaction 2 hours in 1 hour again.The centrifugal washing and drying of reaction product is obtained polyvinyl butyral resin, then it is dissolved in the polyvinyl butyral acetal solution of making mass concentration 10% in the methyl alcohol, solvent temperature is controlled at 55 ℃, be cooled to afterwards 45 ℃, add hydrochloric acid and butyraldehyde-n, its quality of material is than being polyvinyl butyral resin: butyraldehyde-n: hydrochloric acid=5:4:2, temperature of reaction is controlled at 45 ℃, then be warming up to gradually 75 ℃ with 1 hour, reacted 4 hours, completely reacted polyvinyl butyral acetal solution is delivered to high speed dispersor, slowly add pure water, polyvinyl butyral resin is separated out, repeatedly change water washing again and separate out, then centrifugal drying makes the polyvinyl butyral resin finished product.
Table 1
Can find out that according to table 1 the present invention is in industrial utilizability:
Polyvinyl butyral resin tap density of the present invention is large, degree of acetalization is high, good fluidity, synthetic method is simple and easy to control, the little cost of subsequent processes difficulty is low, the product of producing can satisfy the fields such as windshield, building safety glass and solar cell to the requirement of polyvinyl butyral resin, so present method can be used as the polyvinyl butyral resin production of resins in the fields such as windshield, building safety glass and solar cell.
Claims (2)
1. the preparation method of a high degree of acetalization, high workability polyvinyl butyral resin is characterized in that, the method comprises the steps:
1) condensation reaction:
At first, polyvinyl alcohol is warmed up to 95 ℃ is dissolved in water to be made into concentration be 10% solution, this solution is cooled to 40-60 ℃ add butyraldehyde-n and react;
Secondly, described reaction mixture is cooled to 20-25 ℃, add catalyzer hydrochloric acid, insulation reaction at least 1 hour is delivered to reaction mixture condensation two stills again, is warming up to gradually 35-40 ℃ at 1 hour, insulation reaction is 1 hour again, again be warming up to gradually 50-55 ℃ with 1 hour afterwards, insulation reaction is 1 hour again, then cools to room temperature;
2) neutralizing treatment: described cooled reaction solution is delivered to washing kettle washing 5-6 time, is warming up to afterwards 40-50 ℃, add an amount of caustic soda soln and regulate pH value to 8-10, be incubated again 2-3 hour, fully neutralization deacidification;
3) dehydration, drying: the reaction solution after the described neutralization deacidification is washed 6-8 time again by namely making described polyvinyl butyral resin finished product behind the centrifuge dewatering after water ratio enters the cyclone dryer drying less than 30% with air-flow.
2. the preparation method of high degree of acetalization according to claim 1, high workability polyvinyl butyral resin, it is characterized in that: the mass ratio of polyvinyl alcohol, butyraldehyde-n, hydrochloric acid and water is 100:58-60:48-50:900-1000 in the described condensation reaction; The mass concentration of described hydrochloric acid is 30-35%.
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| CN106752996A (en) * | 2016-12-22 | 2017-05-31 | 浙江德斯泰新材料股份有限公司 | Ultraviolet and ultrared PVB films and preparation method thereof can simultaneously be intercepted |
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| CN108299578A (en) * | 2018-01-26 | 2018-07-20 | 内蒙古双欣环保材料股份有限公司 | A kind of high acetalizing degree polyvinyl butyral resin and preparation method thereof |
| CN108822311A (en) * | 2018-05-30 | 2018-11-16 | 天津摩根坤德高新科技发展有限公司 | A kind of colour polyvinyl butyral airsetting bond paper facing production method |
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| CN111087498A (en) * | 2019-11-01 | 2020-05-01 | 上海应用技术大学 | Preparation method of high-quality polyvinyl butyral |
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| CN104059189A (en) * | 2014-06-13 | 2014-09-24 | 浙江德斯泰塑胶有限公司 | Preparation method of photovoltaic special polyvinyl butyral (PVB) resin |
| CN104045751A (en) * | 2014-07-02 | 2014-09-17 | 四川宝利丰科技有限公司 | Preparation method of polyvinyl butyral |
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| CN108299578A (en) * | 2018-01-26 | 2018-07-20 | 内蒙古双欣环保材料股份有限公司 | A kind of high acetalizing degree polyvinyl butyral resin and preparation method thereof |
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| CN110698575A (en) * | 2019-10-28 | 2020-01-17 | 怀集县怀德新材料有限公司 | Preparation method of PVB resin with high bulk density |
| CN111087498A (en) * | 2019-11-01 | 2020-05-01 | 上海应用技术大学 | Preparation method of high-quality polyvinyl butyral |
| CN113429501A (en) * | 2021-07-15 | 2021-09-24 | 湖州鑫富新材料有限公司 | Production method of PVB resin |
| CN113845609A (en) * | 2021-08-26 | 2021-12-28 | 忠信（清远）光伏材料科技有限公司 | Preparation method of polyvinyl butyral |
| CN113845609B (en) * | 2021-08-26 | 2022-04-08 | 忠信（清远）光伏材料科技有限公司 | Preparation method of polyvinyl butyral |
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