CN103012633B - 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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- CN103012633B CN103012633B CN201210541486.0A CN201210541486A CN103012633B CN 103012633 B CN103012633 B CN 103012633B CN 201210541486 A CN201210541486 A CN 201210541486A CN 103012633 B CN103012633 B CN 103012633B
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- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 title claims abstract description 49
- 229920005989 resin Polymers 0.000 title claims abstract description 48
- 239000011347 resin Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 75
- 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
- 238000005406 washing Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001035 drying Methods 0.000 claims abstract description 14
- 238000006359 acetalization reaction Methods 0.000 claims abstract description 12
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 11
- 238000009833 condensation Methods 0.000 claims abstract description 10
- 230000005494 condensation Effects 0.000 claims abstract description 10
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000006482 condensation reaction Methods 0.000 claims abstract description 8
- 230000003472 neutralizing effect Effects 0.000 claims abstract description 4
- 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
- 230000018044 dehydration Effects 0.000 abstract description 2
- 238000006297 dehydration reaction Methods 0.000 abstract description 2
- 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
- 238000002156 mixing Methods 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
- 238000010189 synthetic method Methods 0.000 description 3
- 239000004902 Softening Agent Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000006185 dispersion Substances 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
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 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
- 238000012856 packing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 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
- 238000003786 synthesis reaction 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 the transparency, film-forming properties, winter hardiness, shock resistance, uvioresistant and with the cohesiveness of glass, pottery etc. in there is high-performance.Polyvinyl butyral acetal is the indispensable material preparing laminated safety glass, along with automobile industry, construction industry, the development of photovoltaic industry, the consumption of laminated safety glass is increasing, the demand of China market to polyvinyl butyral resin is increasing, but domestic do not have producer to supply, overwhelming majority dependence on import, and mainly by U.S. Meng Shan all, Du Pont and this three major company of Japanese ponding monopolized, therefore the invention of the synthetic method of this polyvinyl butyral resin, break external technical monopoly, breach the passive situation of the long-term dependence on import of pvb film.
The synthetic method of China Patent No. 201210161377.6 polyvinyl butyral resin is raw material with polyvinyl alcohol and butyraldehyde-n, take hydrochloric acid as catalyzer through low temperature continuous condensating and the polyvinyl butyral resin that again obtains after condensation reaction.In this method, first be low temperature continuous condensating, the butyraldehyde-n of polyvinyl alcohol and appropriate material ratio, hydrochloric acid are started to react in 0 DEG C, then be warming up to 35 DEG C gradually and continue reaction 2 hours, afterwards by the butyraldehyde-n of the resin and the leftover materials ratio that generate, mixed in hydrochloric acid in methyl alcohol, in 45-75 DEG C of reaction 4 hours, obtain the polyvinyl butyral resin of degree of acetalization > 78% through aftertreatment.But the 45-75 DEG C of reaction that be directly warming up in this law easily causes product macromolecular chain rupture thus affect product strength and stability for 4 hours, causes processing film forming need improve the usage quantity of processing temperature or softening agent, processing difficulties and cost is high.
Summary of the invention
Object of the present invention is intended to the shortcoming overcoming the existence of above-mentioned prior art, the preparation method of a kind of high degree of acetalization, high workability polyvinyl butyral resin is provided, the degree of acetalization that the method prepares the polyvinyl butyral resin of gained is high, good fluidity, and production process is simple, need not secondary mixing secondary charging, work flow is short, inflammable and explosive solvent methanol need not be used, safety and environmental protection.
In order to realize the object 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 one, condensation reaction:
First, polyvinyl alcohol is warmed up to 95 DEG C and is dissolved in water and is made into the solution that concentration is 10%, this solution is cooled to 40-60 DEG C and add butyraldehyde-n and react;
Secondly, described reaction mixture is cooled to 20-25 DEG C, add hydrochloric, insulation reaction at least 1 hour, then reaction mixture is delivered to condensation two still, be warming up to 35-40 DEG C gradually at 1 hour, insulation reaction 1 hour again, again be warming up to 50-55 DEG C gradually with 1 hour afterwards, then insulation reaction 1 hour, then cool to room temperature;
Step 2, neutralizing treatment: described cooled reaction solution is delivered to washing kettle washing 5-6 time, is warming up to 40-50 DEG C afterwards, add appropriate caustic soda soln and regulate pH value to 8-10, then be incubated 2-3 hour, fully neutralize deacidification;
Step 3, dehydration, drying: after centrifuge dewatering, be less than 30% to water ratio after again 6-8 time is washed to the reaction solution after described neutralization deacidification and enter after cyclone dryer drying with air-flow and namely obtain described polyvinyl butyral resin finished product.
Further, in described condensation reaction, the mass ratio of polyvinyl alcohol, butyraldehyde-n, hydrochloric acid and water is 100:58-60:48-50:900-1000; 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 progress:
1) in described preparation method, the temperature of reaction mass polyvinyl alcohol and butyraldehyde-n mixing is 40-60 DEG C, butyraldehyde is in disposable whole input polyvinyl alcohol solution, because butyraldehyde is slightly soluble in water, solution surface dispersion is floated on irregular add polyvinyl alcohol water solution solution under low temperature (0-10 DEG C) after, local is easily caused to cross fast response, formation gel lumps, and add when polyvinyl alcohol water solution is cooled to 40-60 DEG C, in continuation cooling mixing process, dispersion effect is good, mixing of materials is even, the resin caking of generation can be reduced greatly, the degree of uniformity of good raising resin-oatmeal, product compaction rate is high, packing density > 2.0g/cm can be obtained
3polyvinyl butyral resin.
2) involved in described preparation method normal-temperature continuous condensation compared with the prior art, after initial reaction temperature brings up to normal temperature (20-25 DEG C) by low temperature (0-10 DEG C), speed of response is accelerated, polyvinyl alcohol molecule chain easily launches simultaneously, functional group exposes, activity is high, and the motion of small molecules butyraldehyde is active, easy generation condensation reaction, product very easily reaches higher degree of acetalization content, again by the intensification condensation of multistep, slaking is stablized, and very easily obtains the polyvinyl butyral resin of degree of acetalization > 80%.
3) involved in described preparation method normal-temperature continuous condensation compared with the prior art, after initial reaction temperature brings up to normal temperature (20-25 DEG C) by low temperature (0-10 DEG C), the expansion that products molecule chain is larger can be ensured, the more butyraldehyde group of condensation, acetalation can not be curled after completing at a higher temperature, the product butyraldehyde Ji Gengyi of synthesis exposes, very easily there is better plastification with softening agent, good fluidity, continuous several times intensification condensation not only can better prevent resin-bonded than condensation under being once raised to high temperature in addition, and can reduce due to the too fast product macromolecular chain fracture caused that heats up greatly, have influence on the stability of product.
4) in the condensation reaction in described preparation method, the mass concentration of the hydrochloric acid that the mass ratio of polyvinyl alcohol, butyraldehyde-n, hydrochloric acid and water uses for 100:58-60:48-50:900-1000(is 30-35%), the hydrochloric of very high percentage is employed in formula, concentration and the homogeneity of solution acid in large-size reactor can be ensured, ensure reactor product homogeneity, be conducive to the mobility improving polyvinyl butyral resin, the polyvinyl butyral resin of melting index > 1.5g/10Min after building-up process terminates, can be obtained.
5) reaction terminate after at 40-50 DEG C neutralizing treatment, the polyvinyl butyral resin molecular chain generated easily launches, the hydrochloric acid small molecules sticking to molecular chain surface is very easily neutralized by the alkali being added, and reduces the number of times of product washing, can obtain stable polyvinyl butyral resin.
To sum up, invention increases the tap density of polyvinyl butyral resin, degree of acetalization and mobility, also improve a lot to the stability of product, what the product also having this invention technology to obtain can be fabulous is applied to automobile industry, construction industry and photovoltaic industry, and profit margin is large.
The present invention can be well understood to further by specific embodiments of the invention given below.But they are not limitation of the invention.
Embodiment
Embodiment 1
Polyvinyl alcohol 100g being warmed up to 95 DEG C is dissolved in 900g water, cool to 45 DEG C of butyraldehyde-ns adding whole ratio again, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to temperature of reaction 20 DEG C, add the hydrochloric acid of whole ratio, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 35 DEG C gradually with 1 hour, insulation reaction 1 hour, again be warming up to 50 DEG C gradually with 1 hour afterwards, insulation reaction 1 hour, then after cooling down, reaction product is washed 6 times, be warming up to 45 DEG C afterwards, add appropriate caustic soda soln and regulate PH to 9, be incubated 2 hours, abundant neutralization deacidification, last washing again 8 times, polyvinyl butyral resin after washing obtains polyvinyl butyral resin finished product through centrifugal drying.
Embodiment 2
Polyvinyl alcohol 100g being warmed up to 95 DEG C is dissolved in 900g water, cool to 45 DEG C of butyraldehyde-ns adding whole ratio again, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to temperature of reaction 25 DEG C, add the hydrochloric acid of whole ratio, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 40 DEG C gradually with 1 hour, insulation reaction 1 hour, again be warming up to 55 DEG C gradually with 1 hour afterwards, insulation reaction 1 hour, then after cooling down, reaction product is washed 6 times, be warming up to 45 DEG C afterwards, add appropriate caustic soda soln and regulate PH to 9, be incubated 2 hours, abundant neutralization deacidification, last washing again 8 times, polyvinyl butyral resin after washing obtains polyvinyl butyral resin finished product through centrifugal drying.
Embodiment 3
Polyvinyl alcohol 100g being warmed up to 95 DEG C is dissolved in 900g water, cool to 45 DEG C of butyraldehyde-ns adding whole ratio again, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to temperature of reaction 20 DEG C, add the hydrochloric acid of whole ratio, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 35 DEG C gradually with 1 hour, insulation reaction 1 hour, again be warming up to 50 DEG C gradually with 1 hour afterwards, insulation reaction 1 hour, then after cooling down, reaction product is washed 6 times, be warming up to 45 DEG C afterwards, add a small amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, abundant neutralization deacidification, last washing again 8 times, polyvinyl butyral resin after washing obtains polyvinyl butyral resin finished product through centrifugal drying.
Embodiment 4
Polyvinyl alcohol 100g being warmed up to 95 DEG C is dissolved in 900g water, cool to 45 DEG C of butyraldehyde-ns adding whole ratio again, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to temperature of reaction 25 DEG C, add the hydrochloric acid of whole ratio, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 40 DEG C gradually with 1 hour, insulation reaction 1 hour, again be warming up to 55 DEG C gradually with 1 hour afterwards, insulation reaction 1 hour, then after cooling down, reaction product is washed 6 times, be warming up to 55 DEG C afterwards, add a small amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, abundant neutralization deacidification, last washing again 8 times, polyvinyl butyral resin after washing obtains polyvinyl butyral resin finished product through centrifugal drying.
Comparative example 1
Polyvinyl alcohol 100g being warmed up to 95 DEG C is dissolved in 900g water, cool to 20 DEG C of butyraldehyde-ns adding whole ratio again, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, the hydrochloric acid of whole ratio is added after stirring half hour, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 35 DEG C gradually with 1 hour, insulation reaction 1 hour, again be warming up to 50 DEG C gradually with 1 hour afterwards, insulation reaction 1 hour, then after cooling down, reaction product is washed 6 times, be warming up to 45 DEG C afterwards, add appropriate caustic soda soln and regulate PH to 9, be incubated 2 hours, abundant neutralization deacidification, last washing again 8 times, polyvinyl butyral resin after washing obtains polyvinyl butyral resin finished product through centrifugal drying.
Comparative example 2
Polyvinyl alcohol 100g being warmed up to 95 DEG C is dissolved in 900g water, cool to 45 DEG C of butyraldehyde-ns adding whole ratio again, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to temperature of reaction 5 DEG C, add the hydrochloric acid of whole ratio, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again reaction solution was warming up to 40 DEG C gradually with 1 hour, insulation reaction 1 hour, again be warming up to 55 DEG C gradually with 1 hour afterwards, insulation reaction 1 hour, then after cooling down, reaction product is washed 6 times, be warming up to 45 DEG C afterwards, add appropriate caustic soda soln and regulate PH to 9, be incubated 2 hours, abundant neutralization deacidification, last washing again 8 times, polyvinyl butyral resin after washing obtains polyvinyl butyral resin finished product through centrifugal drying.
Comparative example 3
Polyvinyl alcohol 100g being warmed up to 95 DEG C is dissolved in 900g water, cool to 45 DEG C of butyraldehyde-ns adding whole ratio again, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n=100:60, then reaction mixture is continued to be cooled to temperature of reaction 20 DEG C, add the hydrochloric acid of whole ratio, its reaction mass mass ratio is polyvinyl alcohol: hydrochloric acid=100:50, hydrochloric acid mass concentration is 32%, insulation reaction 1 hour, again by reaction solution with being rapidly heated half an hour to 50 DEG C, insulation reaction 2 hours, then after cooling down, reaction product is washed 6 times, be warming up to 45 DEG C afterwards, add a small amount of caustic soda soln and regulate PH to 9, be incubated 2 hours, abundant neutralization deacidification, last washing again 8 times, polyvinyl butyral resin after washing obtains polyvinyl butyral resin finished product through centrifugal drying.
Comparative example 4
Polyvinyl alcohol 100g is warmed up to 95 DEG C be dissolved in 900g water, adds appropriate hydrochloric acid and butyraldehyde-n, its reaction mass mass ratio is polyvinyl alcohol: butyraldehyde-n: hydrochloric acid=8:4:3, and hydrochloric acid mass concentration is 32%; Wherein butyraldehyde-n drops at twice, and twice input ratio is 1:1.Its concrete rate-determining steps is, when condensation kettle greenhouse cooling to 5 DEG C, throw hydrochloric acid and butyraldehyde-n, question response, after 1 hour, drops into butyraldehyde-n again, waits after reacting 1 hour again with within 1 hour, being warming up to 35 DEG C of insulation reaction 2 hours more gradually.Centrifugal for reaction product washing and drying is obtained polyvinyl butyral resin, then it is dissolved in methyl alcohol the polyvinyl butyral solution making mass concentration 10%, solvent temperature controls at 55 DEG C, be cooled to 45 DEG C afterwards, 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 controls at 45 DEG C, then 75 DEG C were warming up to gradually with 1 hour, react 4 hours, completely reacted polyvinyl butyral solution is delivered to high speed dispersor, slowly add pure water, polyvinyl butyral resin is separated out, repeatedly change water washing again to separate out, then centrifugal drying obtains polyvinyl butyral resin finished product.
Table 1
The present invention's utilizability industrially can be found out according to table 1:
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 produced can meet the fields such as windshield, building safety glass and solar cell to the requirement of polyvinyl butyral resin, and therefore 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 (1)
1. a preparation method for high degree of acetalization, high workability polyvinyl butyral resin, it is characterized in that, the method comprises the steps:
1) condensation reaction:
First, polyvinyl alcohol is warmed up to 95 DEG C and is dissolved in water and is made into the solution that concentration is 10%, this solution is cooled to 40-60 DEG C and add butyraldehyde-n and react;
Secondly, described reaction mixture is cooled to 20-25 DEG C, add hydrochloric, insulation reaction at least 1 hour, then reaction mixture is delivered to condensation two still, be warming up to 35-40 DEG C gradually at 1 hour, insulation reaction 1 hour again, again be warming up to 50-55 DEG C gradually with 1 hour afterwards, then insulation reaction 1 hour, then cool to room temperature;
2) neutralizing treatment: described cooled reaction solution is delivered to washing kettle washing 5-6 time, is warming up to 40-50 DEG C afterwards, adds appropriate caustic soda soln adjust ph to 8-10, then be incubated 2-3 hour, fully neutralize deacidification;
3) dewater, dry: after again 6-8 time is washed to the reaction solution after described neutralization deacidification after centrifuge dewatering to water ratio be less than 30% enter cyclone dryer drying with air-flow after namely obtain described polyvinyl butyral resin finished product;
In described condensation reaction, the mass ratio of polyvinyl alcohol, butyraldehyde-n, hydrochloric acid and water is 100:58-60:48-50:900-1000; The mass concentration of described hydrochloric acid is 30-35%.
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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 |
| 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 |
| CN107129548A (en) * | 2017-06-02 | 2017-09-05 | 忠信（清远）光伏材料科技有限公司 | A kind of preparation method of high fluidity PVB resin |
| 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 |
| 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 |
| CN113429501B (en) * | 2021-07-15 | 2022-04-29 | 湖州鑫富新材料有限公司 | Production method of PVB resin |
| 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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| CN102649825B (en) * | 2012-05-23 | 2014-02-19 | 安徽皖维集团有限责任公司 | High-hydroformylation-degree polyvinyl butyral resin and preparation method thereof |
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