CN107129548A - A kind of preparation method of high fluidity PVB resin - Google Patents
A kind of preparation method of high fluidity PVB resin Download PDFInfo
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- CN107129548A CN107129548A CN201710406582.7A CN201710406582A CN107129548A CN 107129548 A CN107129548 A CN 107129548A CN 201710406582 A CN201710406582 A CN 201710406582A CN 107129548 A CN107129548 A CN 107129548A
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- 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
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- 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
- C08F2800/00—Copolymer characterised by the proportions of the comonomers expressed
- C08F2800/20—Copolymer characterised by the proportions of the comonomers expressed as weight or mass percentages
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Abstract
Have the present invention relates to a kind of preparation method of high fluidity PVB resin, including step：(1) condensation reaction：It is 8 10% solution to be warming up to more than 90 DEG C and be dissolved in water to be made into concentration polyvinyl alcohol A and Type B, the solution is cooled into 5 15 degree, being slowly added into hutanal under catalyst action is allowed to condensation reaction；(2) wash：Reaction solution after the cooling is delivered to washing kettle, washed 56 times with 35 55 DEG C, liquid caustic soda solution is added and adjusts pH value to 10 13；(3) it is dehydrated, dries：Reaction solution after neutralization, is less than 30% to moisture content after centrifuge dewatering, then sloughs remaining moisture by pneumatic conveying drying, that is, the PVB resin finished product is made.The present invention improves the uniformity coefficient of resin-oatmeal, and product compaction rate is high, and curing is stable, easily obtains the PVB resin of acetalizing degree ＞ 80% high stability.
Description
Technical field
The invention belongs to hot shortness's technical field of polymer materials, particularly a kind of preparation side of high fluidity PVB resin
Method.
Background technology
PVB (polyvinyl butyral resin) resins the transparency, film forming, cold resistance, impact resistance and with glass, pottery
There is superior function in terms of the caking property of porcelain etc..PVB resin is the indispensable material for preparing laminated glass, with automobile industry, is built
The development of industry, photovoltaic industry is built, the consumption of laminated safety glass is increasing, China market is more next to the demand of PVB resin
It is bigger, but domestic no producer can supply, most dependence on import, and mainly by U.S. Meng Shan all, Du Pont and Japan
This three major company of ponding is monopolized, therefore the synthesis success of domestic PVB resin, has been broken the technical monopoly of foreign countries, has been breached PVB
Diaphragm relies on the passive situation into product for a long time.
The synthetic method of PVB resin be using polyvinyl alcohol and hutanal as raw material, it is continuous through low temperature by catalyst of hydrochloric acid
Condensation and the PVB resin that condensation reaction is obtained again.In this method, it is low temperature continuous condensating first, by polyvinyl alcohol with fitting
Measure the hutanal of material ratio, hydrochloric acid and start input in low temperature, gradually heat up, be incubated after reaction phase transformation, it is post-treated to obtain acetal
Degree>78% PVB resin.But the above method is easily caused the fracture of product macromolecular chain so as to influence product strength and stability,
Processing temperature or the usage amount of plasticizer need to be improved when causing to be processed into PVB films, high processing costs and yield rate is low.
The content of the invention
The purpose of the present invention is in view of the shortcomings of the prior art, and to propose a kind of preparation method of high fluidity PVB resin.
The present invention solves its technical problem and takes following technical scheme to realize：
A kind of preparation method of high fluidity PVB resin, it is characterised in that comprise the following steps：
(1) condensation reaction：A types polyvinyl alcohol and Type B polyvinyl alcohol are added in deionized water, stirring is warming up to 90 DEG C
More than, the solution that concentration is 8-10% is configured to, wherein, the quality of the A types polyvinyl alcohol accounts for the 1%- of polyvinyl alcohol total amount
10%, the solution is cooled into 5-15 degree, hutanal is slowly added into the presence of hydrochloric and is allowed to carry out condensation reaction,
Wherein, the mass ratio of hydrochloric acid and total polyvinyl alcohol is 12-15:100, hydrochloric acid mass concentration is 31%-40%, and hutanal gathers with total
The mass ratio of vinyl alcohol is 50-58:100, after reaction occurs, 60-70 DEG C was gradually heating within 2-3 hours, the temperature is maintained
Degree 1-3 hours, is subsequently cooled to room temperature；
(2) wash：Reaction solution after the cooling is delivered to washing kettle, washed 5-6 times with 35-55 DEG C, liquid caustic soda is added
Solution adjusts pH value to 10-13；
(3) it is dehydrated, dries：Reaction solution after neutralization, is less than 30% to moisture content after centrifuge dewatering, then passes through gas
Remaining moisture is sloughed in stream drying, that is, the PVB resin finished product is made.
Moreover, in the step (1), 60-70 DEG C is being warming up to, and after maintaining the temperature 1-3 hours, add alkali lye with thorough
Bottom terminating reaction.
Moreover, in step (1), the A types polyvinyl alcohol is polyvinyl alcohol of the molecular weight between 20000-30000；
The Type B polyvinyl alcohol is polyvinyl alcohol of the molecular weight between 70000-80000.
Moreover, in the step (2), to ensure that washing is thorough, after being washed with 35-55 DEG C, 0.5-1h is kept, then with cold
Washing 3-8 times.
Advantages and positive effects of the present invention are：
1st, the temperature that reaction mass polyvinyl alcohol and hutanal are mixed in preparation method of the present invention is 5-15 DEG C, and hutanal is
In disposable all inputs poly-vinyl alcohol solution, dispersion effect is good in mixed process, and material is well mixed, and can be significantly reduced
Resin caking is generated, the uniformity coefficient of resin-oatmeal is improved well, product compaction rate is high, can obtain packing density 1.3-
1.8g/cm3PVB resin.
2nd, compared with the prior art, initial reaction temperature is by low for normal-temperature continuous involved in preparation method of the present invention condensation
It is warm 5-15 DEG C improve temperature arrive 20-25 DEG C after, reaction speed quickening, while polyvinyl alcohol molecule chain easily deploys, functional group is sudden and violent
Dew, activity are high, easily occur condensation reaction, product easily reaches higher acetalizing degree content, then is condensed by the heating of multistep, curing
It is stable, easily obtain acetalizing degree ＞ 80% PVB resin.
3rd, compared with the prior art, initial reaction temperature is by low for normal-temperature continuous involved in preparation method of the present invention condensation
5-15 DEG C of temperature improves temperature and arrived after 20-25 DEG C, it is ensured that the bigger expansion of products molecule chain, the more butyraldehyde bases of condensation
Group, will not curl after acetalation is complete at a higher temperature, and the product butyraldehyde base of synthesis is more easy to exposure, easily occurs more with plasticizer
Good plasticization, good fluidity, after being incubated 1-3 hours, heating condensation not only can preferably prevent resin-bonded, while can
So that the reaction of product macromolecular chain is uniform, make the stability of product more preferable.
4th, the hydrochloric of very high percentage has been used in preparation method formula of the present invention, it is ensured that in large-size reactor
The concentration and uniformity of solution acid, it is ensured that reactor product homogeneity, are conducive to improving the mobility of PVB resin, building-up process knot
Melt index 1.2-1.8g/10min PVB resin is can obtain after beam.
5th, in preparation method of the present invention, reaction terminates, after carrying out neutralisation treatment at 40-50 DEG C, to generate PVB resin molecule
Chain easily deploys, and the hydrochloric acid small molecule for sticking to strand surface is easily neutralized by alkali, reduces the number of times of product washing, can obtain
To stable PVB resin.
6th, the present invention improves the mobility of PVB resin, and the stability to product also improves a lot, obtained product energy
Fabulous is applied to automobile industry, building trade and photovoltaic industry, and profit margin is big.
Embodiment
The embodiment of the present invention is further described below：It is emphasized that embodiment of the present invention is explanation
Property, rather than it is limited, therefore the present invention is not limited to the embodiment described in embodiment, it is every by this area
The other embodiment that technical staff's technique according to the invention scheme is drawn, also belongs to the scope of protection of the invention.
Embodiment 1
A types and the common 125g of Type B polyvinyl alcohol are added in 1340ml deionized waters, the quality of A type polyvinyl alcohol is poly- second
The 1-5% of enol total amount, is persistently stirred and is warming up to 90-98 DEG C, and is incubated 30-100min, and solution is cooled into 5-10 DEG C, plus
Enter hydrochloric acid, put into hutanal, the mass ratio of hydrochloric acid and total polyvinyl alcohol is 12-15:100, hydrochloric acid mass concentration 35%, hutanal
Mass ratio with total polyvinyl alcohol is 50-58:100, after reaction occurs, within 2-3 hours, it is warming up to 60-70 DEG C, Zhi Houbao
Temperature, adds sodium hydroxide terminating reaction, is washed afterwards, first with 35-45 DEG C of hot water wash 5-6 times, adds a small amount of hydrogen-oxygen
Change sodium regulation pH to 10-13, keep 0.5-1h, then washed 3-8 times with cold water, the polyvinyl butyral resin after washing is through dehydration
Dry, obtain polyvinyl butyral resin finished product.
Wherein, the A types polyvinyl alcohol is polyvinyl alcohol of the molecular weight between 20000-30000；The Type B polyethylene
Alcohol is polyvinyl alcohol of the molecular weight between 70000-80000.
Embodiment 2
A types and the common 105g of Type B polyvinyl alcohol are added in 1340ml deionized waters, the amount of A type polyvinyl alcohol is polyethylene
The 5-10% of alcohol total amount, is persistently stirred and is warming up to more than 90 DEG C, and is incubated 30-100min, and solution is cooled into 5-10 DEG C, plus
Enter hydrochloric acid, put into hutanal, the mass ratio of hydrochloric acid and total polyvinyl alcohol is 12-15:100, hydrochloric acid mass concentration 31%, hutanal
Mass ratio with total polyvinyl alcohol is 50-58:100, after reaction occurs, within 2-3 hours, it is warming up to 60-70 DEG C, Zhi Houbao
Temperature, adds sodium hydroxide terminating reaction, is washed afterwards, first with 35-45 DEG C of hot water wash 5-6 times, adds a small amount of hydrogen-oxygen
Change sodium regulation pH to 10-13, keep 0.5-1h, then washed 3-8 times with cold water, the polyvinyl butyral resin after washing is through vertical letter
Dehydrate, obtain polyvinyl butyral resin finished product.
Comparative example 1
A types and the common 132g of Type B polyvinyl alcohol are added in 1340ml deionized waters, the amount of A type polyvinyl alcohol is polyethylene
The 1-5% of alcohol total amount, is persistently stirred and is warming up to 90-98 DEG C, and is incubated 30-100min, and solution is cooled into 12-15 DEG C, plus
Enter hydrochloric acid, put into hutanal, the mass ratio of hydrochloric acid and total polyvinyl alcohol is 12-15:100, hydrochloric acid mass concentration 40%, hutanal
Mass ratio with total polyvinyl alcohol is 50-58:100, after reaction occurs, within 2-3 hours, it is warming up to 60-70 DEG C, Zhi Houbao
Temperature, adds appropriate sodium hydroxide terminating reaction, is washed afterwards, first with 35-55 DEG C of hot water wash 5-6 times, adds and lacks
Sodium hydroxide is measured, pH to 10-13 is adjusted, 0.5-1h is kept, then washed 3-8 times with cold water, the polyvinyl butyral resin tree after washing
Fat obtains polyvinyl butyral resin finished product through dehydrating.
Comparative example 2
A types and the common 125g of Type B polyvinyl alcohol are added in 1340ml deionized waters, the amount of A type polyvinyl alcohol is polyethylene
The 5-10% of alcohol total amount, persistently stirs and is warming up to more than 95 DEG C, and be incubated 60min.Solution is cooled to 12-15 DEG C, addition
The mass ratio of hydrochloric acid, input hutanal, hydrochloric acid and total polyvinyl alcohol is 12-15:100, hydrochloric acid mass concentration 35%, hutanal with
The mass ratio of total polyvinyl alcohol is 50-58:100, after reaction occurs, within 2-3 hours, it is warming up to 60-70 DEG C, Zhi Houbao
Temperature, adds appropriate sodium hydroxide terminating reaction, is washed afterwards, first with 35-45 DEG C of hot water wash 5-6 times, adds and lacks
Sodium hydroxide is measured, pH to 10-13 is adjusted, 0.5-1h is kept, then washed 3-8 times with cold water, the polyvinyl butyral resin tree after washing
Fat obtains polyvinyl butyral resin finished product through dehydrating.
According to upper table, it can be seen that the utilizability of the present invention industrially
Polyvinyl butyral resin bulk density of the invention is moderate, acetalizing degree is high, good fluidity, and synthetic method is simple
It is easily controlled, the small cost of subsequent treatment difficulty is low, the product of production can meet windshield, building safety glass and too
The requirements of the field to polyvinyl butyral resin such as positive energy battery, therefore this method may be used as windshield, building
The polyvinyl butyral resin production in the field such as safety glass and solar cell.
Claims (4)
1. a kind of preparation method of high fluidity PVB resin, it is characterised in that comprise the following steps：
(1) condensation reaction：A types polyvinyl alcohol and Type B polyvinyl alcohol are added in deionized water, stirring be warming up to 90 DEG C with
On, the solution that concentration is 8-10% is configured to, wherein, the quality of the A types polyvinyl alcohol accounts for the 1%- of polyvinyl alcohol total amount
10%, the solution is cooled into 5-15 degree, hutanal is slowly added into the presence of hydrochloric and is allowed to carry out condensation reaction,
Wherein, the mass ratio of hydrochloric acid and total polyvinyl alcohol is 12-15:100, hydrochloric acid mass concentration is 31%-40%, and hutanal gathers with total
The mass ratio of vinyl alcohol is 50-58:100, after reaction occurs, 60-70 DEG C was gradually heating within 2-3 hours, the temperature is maintained
Degree 1-3 hours, is subsequently cooled to room temperature；
(2) wash：Reaction solution after the cooling is delivered to washing kettle, washed 5-6 times with 35-55 DEG C, liquid caustic soda solution is added
PH value is adjusted to 10-13；
(3) it is dehydrated, dries：Reaction solution after neutralization, is less than 30% after centrifuge dewatering to moisture content, then dry by air-flow
It is dry to slough remaining moisture, that is, the PVB resin finished product is made.
2. the preparation method of high fluidity PVB resin according to claim 1, it is characterised in that：In the step (1),
It is being warming up to 60-70 DEG C, and after maintaining the temperature 1-3 hours, is adding alkali lye with thorough terminating reaction.
3. the preparation method of high fluidity PVB resin according to claim 1, it is characterised in that：In step (1), institute
It is polyvinyl alcohol of the molecular weight between 20000-30000 to state A type polyvinyl alcohol；The Type B polyvinyl alcohol is that molecular weight exists
Polyvinyl alcohol between 70000-80000.
4. the preparation method of high fluidity PVB resin according to claim 1, it is characterised in that：In the step (2),
To ensure that washing is thorough, after being washed with 35-55 DEG C, 0.5-1h is kept, then washed 3-8 times with cold water.
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| CN201710406582.7A CN107129548A (en) | 2017-06-02 | 2017-06-02 | A kind of preparation method of high fluidity PVB resin |
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| CN201710406582.7A CN107129548A (en) | 2017-06-02 | 2017-06-02 | A kind of preparation method of high fluidity PVB resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109593144A (en) * | 2018-12-12 | 2019-04-09 | 怀集县怀德新材料有限公司 | A kind of PVB resin powder, preparation method thereof that comprehensive performance is high |
| CN109627364A (en) * | 2018-12-12 | 2019-04-16 | 怀集县怀德新材料有限公司 | A kind of PVB resin powder of automotive grade and preparation method thereof |
| CN111087498A (en) * | 2019-11-01 | 2020-05-01 | 上海应用技术大学 | Preparation method of high-quality polyvinyl butyral |
| CN111690083A (en) * | 2020-07-28 | 2020-09-22 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl butyral resin |
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| CN103012633A (en) * | 2012-12-13 | 2013-04-03 | 浙江德斯泰塑胶有限公司 | Preparation method of high-acetalization-degree high-flowability polyvinyl butyral resin |
| CN103007587A (en) * | 2012-11-28 | 2013-04-03 | 浙江杭州鑫富药业股份有限公司 | Emulsifying defoaming system and PVB (Polyvinyl Butyral) resin production method employing the same |
| CN103172769A (en) * | 2013-04-24 | 2013-06-26 | 隆回群丰生物化工有限公司 | Preparation method of high-viscosity ultra-high molecular weight polyvinyl butyral resin |
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2017
- 2017-06-02 CN CN201710406582.7A patent/CN107129548A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103007587A (en) * | 2012-11-28 | 2013-04-03 | 浙江杭州鑫富药业股份有限公司 | Emulsifying defoaming system and PVB (Polyvinyl Butyral) resin production method employing the same |
| CN103012633A (en) * | 2012-12-13 | 2013-04-03 | 浙江德斯泰塑胶有限公司 | Preparation method of high-acetalization-degree high-flowability polyvinyl butyral resin |
| CN103172769A (en) * | 2013-04-24 | 2013-06-26 | 隆回群丰生物化工有限公司 | Preparation method of high-viscosity ultra-high molecular weight polyvinyl butyral resin |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109593144A (en) * | 2018-12-12 | 2019-04-09 | 怀集县怀德新材料有限公司 | A kind of PVB resin powder, preparation method thereof that comprehensive performance is high |
| CN109627364A (en) * | 2018-12-12 | 2019-04-16 | 怀集县怀德新材料有限公司 | A kind of PVB resin powder of automotive grade and preparation method thereof |
| CN111087498A (en) * | 2019-11-01 | 2020-05-01 | 上海应用技术大学 | Preparation method of high-quality polyvinyl butyral |
| CN111690083A (en) * | 2020-07-28 | 2020-09-22 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl butyral resin |
| CN111690083B (en) * | 2020-07-28 | 2023-10-03 | 安徽皖维高新材料股份有限公司 | Preparation method of polyvinyl butyral resin |
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