CN108409897A - A kind of method that microwave radiation technology efficiently produces PVB resin powder - Google Patents
A kind of method that microwave radiation technology efficiently produces PVB resin powder Download PDFInfo
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- CN108409897A CN108409897A CN201810165417.1A CN201810165417A CN108409897A CN 108409897 A CN108409897 A CN 108409897A CN 201810165417 A CN201810165417 A CN 201810165417A CN 108409897 A CN108409897 A CN 108409897A
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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
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
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Abstract
The invention discloses a kind of method that microwave radiation technology efficiently produces PVB resin powder, be added PVA solution, aldehyde, catalyst reactor in the heating process of aldolisation occurs, to have used frequency be 3 × 108Hertz ~ 3 × 1011The microwave of hertz is a kind of heat source of reaction system, it changes previous all using the single heat transfer mode of heating such as external resistance wire, cycling hot water jacket, the aldolisation time can not only be reduced, it can also be precisely controlled aldolisation temperature, improve the qualities such as acetalizing degree, hydroxyl distributing homogeneity, the lot stability of product PVB resin powder.
Description
Technical field
The present invention relates to a kind of methods that microwave radiation technology efficiently produces PVB resin powder, belong to high molecular material manufacturing field.
Background technology
PVB resin powder is to manufacture automobile, photovoltaic, the doubling glass PVB intermediate coats such as building to use raw material, full name in English
It is polyvinyl butyral, Chinese is polyvinyl butyral.Current Japan's ponding, Kuraray, her scholar of the U.S.
Graceful three international chemical industry giants have not only monopolized the production of global high-quality PVB resin powder, but also stringent blocking technology and external
Refusal sells this kind of PVB resin powder, maintains it in the monopoly profits in high-end PVB intermediate coats field for a long time according to this.And China is current
Although there is about 30 chemical enterprises that can also produce PVB resin powder, its quality is relatively low, is only used for building, ink
And the low-end markets such as coating.
In addition to acetal radical, unreacted hydroxyl, also remaining vinyl acetate-based in the chemical constitution of PVB resin powder
Group.The PVB molecules of high-quality should have many characteristics, such as high acetalizing degree, hydroxyl be evenly distributed, without package, impurity is few, batch is stablized,
And these targets that exactly current domestic manufacturer is difficult to realize.Someone by the synthesis technology of PVB resin powder be classified as one-step method,
Dissolution method, the precipitation method, homogeneous alcohol method, also someone it is classified as homogeneous method, multi-phases process etc., but the PVB in all techniques
Composition principle is all summed up as aldolisation：Under the action of catalyst, hydroxyl and aldehyde generation acetal are anti-in polyvinyl alcohol (PVA)
It should obtain product PVB, wherein raw material PVA can be that the polyvinyl acetate after alcoholysis can also be solid polyvinyl alcohol
PVA usually will be first dissolved in water, methanol, ethyl alcohol equal solvent convenient for being contacted with aldehyde by grain, to be smoothed out the aldolisation,
Stringent controlling reaction temperature is needed, later stage needs is especially reacted and heats to promote to react and improve acetalizing degree.However, the acetal
To reaction temperature quite sensitive, the too low acetalizing degree that can make PVB resin powder of temperature is insufficient and reduces the mechanical property of PVB films for reaction
Can, temperature is excessively high and PVB resin powder hydroxyl can be made to be unevenly distributed and product is caused to wrap up a large amount of impurity at blocky be quickly precipitated,
Therefore in all kinds of techniques of synthesis PVB resin powder, it is the key that obtain high-quality PVB resin powder to be precisely controlled reaction temperature.
Current most of producers both at home and abroad all use the stainless steel kettle of intermittent feeds（It matches ceramic-lined）As the anti-of aldolisation
Device is answered, in addition, patent CN201120214100 discloses a kind of tubular reactor that continous way feeds intake, patent
CN201510080655 discloses a kind of micro-tubular reactor that semi continuous feeds intake, it is reported that all can smoothly produce.However, extremely
Modern heat transfer is still unique mode of heating in above-mentioned all reactors, i.e., all producers carry out heating and temperature to late phase reaction object
The heat exchange pattern that heat source-reactor-outer reaction object-internal-response object is all used when degree control, conducts layer by layer from outside to inside
Heat, wherein heat source are usually Resistant heating set, circulating hot water or circulating heat conduction oil etc..However since PVB is the bad of heat
Conductor, heat transfer coefficient is very low, even if the high-speed stirred incessantly of the agitating device in stainless steel cauldron, cannot still improve
The hysteresis quality and temperature gradient that heat is transmitted from outer layer to inside cause the hydroxyl value of reaction product PVB resin powder to be unevenly distributed
It is even, batch is unstable, quality is not high.Also, it is easy that partial material is made to float when high-speed stirred and is adhered on reaction kettle inner wall,
Because stainless steel inner wall relative temperature is higher, causes this partial material to be easy desiccation skinning and forms the very low grit of acetalizing degree,
Later stage, which mixes, reduces quality in product.On the other hand, current many to reduce the negative effect that heat transfer causes heat unevenness
Producer is all meticulous when controlling the aldolisation of PVA and aldehyde, by the way of slowly heating up, when causing entire aldolisation
Between excessively very long, only later stage heating process just at least 4 hours, this not only consumes mass energy but also seriously reduces production effect
Rate.
Microwave（MW, microwave）It is frequency about 3 × 108Hertz ~ 3 × 1011Hertz（300MHz~300GHz）It
Between, i.e. electromagnetic wave of the wavelength within the scope of 100cm to 1mm.Microwave heating is different from heat transfer, and principle is the dipole by medium
Son turns to be heated in vivo caused by the dielectric consume of polarization and interfacial polarization in microwave field, is that polarizable medium is made in microwave field
The movement for being equivalent to " molecule stirring " is generated with its high speed rotation under, to uniformly and quickly be heated, i.e., " interior heating "；
The characteristics of microwave heating is：Speed be exceedingly fast it is efficient, can start or stop in time, inside and outside Synchronous Heating, without heat transfer etc..When
Before, intermittent and continous way industrial microwave reaction kettle, the microwave reaction pipe of prior art maturation, heating frequency have solid on the market
Fixed pattern, also there is a frequency conversion type, heating power has constant, also has adjustable.Many organic high scores can be synthesized using microwave
Sub- material, but according to known to the applicant, so far both at home and abroad in the technique of synthesis PVB resin powder, either skills such as paper, patent
Art document or the specific method of manufacturer, all without the report with microwave heating.
Invention content
Problems to be solved by the invention
During synthesizing PVB resin powder, precisely and it is uniformly controlled the pass that aldolisation temperature is influence product quality quality
Key, conventional heating techniques utilize single heat transfer technology, transmit heat layer by layer from outside to inside, and not only heating time is long, but also
There is apparent temperature gradient in the reaction system, causes the temperature disunity of aldolisation in system, product PVB resin powder
Hydroxyl value is unevenly distributed, batch is unstable, quality is not high.
The solution to the problem
The applicant substitutes previous single heat transfer in the production process of PVB resin powder, using microwave heating technique and heats
Technology is accurately uniformly controlled the temperature of aldolisation system, and chemical equation is as follows：
As the method that a kind of microwave radiation technology in the present invention efficiently produces PVB resin powder, PVA solution, aldehyde, catalyst is being added
Reactor in occur aldolisation heating process in, used frequency be 3 × 108Hertz ~ 3 × 1011The microwave of hertz is made
For a kind of heat source of reaction system, i.e. microwave can be unique mode of heating, can also be and other mode of heatings
A kind of complementary mode of heating, the other mode of heatings that can be enumerated include but is not limited to heat transfer, thermal convection current, ultrasonic wave etc..
It can be the polyvinyl acetate after alcoholysis as the reactant PVA in the present invention, can also be solid polyethylene
Alcohol.Solvent includes but is not limited at least one of water, methanol, ethyl alcohol, isopropanol etc. in PVA solution.
It is at least one of butyraldehyde, n-butanal, isobutylaldehyde, preferably n-butanal as the reactant aldehyde in the present invention.
It is in hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate as the catalyst in the present invention
At least one, preferably hydrochloric acid.
As the reactant in the present invention, PVA solution, butyraldehyde, catalyst be added reactor mode be intermittent, continuous
One kind in formula, semi continuous.Wherein, reactor is at least one in tank reactor, tubular reactor, micro-tubular reactor
Kind, microwave generator, which may be placed inside reactor, reactor outside or reactor inside and outside, setting, microwave generator
Quantity be one or more.
As the substance that reactor is added in the present invention, including but not limited to three kinds of PVA solution, butyraldehyde, catalyst masters
Want reactant, can also selectivity add other auxiliary agents, such as commercially available antioxidant three (2,4- di-t-butyl) phosphorous acid
Phenyl ester, emulsifier polyoxyethylene octyl phenol ether, dispersant dodecyl sodium sulfate etc..
As a kind of heat source in the present invention, the microwave frequency of microwave generator is 3 × 108Hertz ~ 3 × 1011Hertz
Between it is constant, can also be herein within the scope of it is adjustable, the microwave power of microwave generator is 1 watt ~ 1020It is permanent between watt
It is fixed, can also be herein within the scope of it is adjustable.
The effect of invention
The present invention be added PVA solution, aldehyde, catalyst reactor in occur aldolisation heating process in, used frequency
Rate is 3 × 108Hertz ~ 3 × 1011The microwave of hertz heats for it, changes previous all using external resistance wire, circulating hot water
The single heat transfer mode of heatings such as set, can not only reduce the aldolisation time, moreover it is possible to be precisely controlled aldolisation temperature, improve production
The qualities such as acetalizing degree, hydroxyl distributing homogeneity, the lot stability of object PVB resin powder.
Description of the drawings
The flow diagram of the external single microwave generator auxiliary production PVB resin powder of Fig. 1 reaction kettles；
The flow diagram of single microwave generator auxiliary production PVB resin powder built in Fig. 2 reaction kettles；
The flow diagram of multiple microwave generator auxiliary production PVB resin powder built in Fig. 3 reaction kettles；
The flow diagram of the external single microwave generator auxiliary production PVB resin powder of Fig. 4 reaction tubes；
The flow diagram of microwave generator auxiliary production PVB resin powder is all set inside and outside Fig. 5 reaction tubes；
The flow diagram of multiple microwave generator auxiliary production PVB resin powder built in Fig. 6 reaction tubes.
Wherein 11 be dissolution kettle, and 12 be tank reactor, and 13 be microwave generator, and 41 be tubular reactor, and 14 be washing
Kettle, A are PVA solution, and B is aldehyde, and C is catalyst, and D is product PVB resin powder.
Specific implementation mode
Embodiment 1
In the stainless steel dissolution kettle that a volume is 1 ton, 540 kilograms of deionized water is added in the PVA particles of 60 kilograms of input
And 95 DEG C are heated to, mechanical agitation forms PVA aqueous solutions after so that solid particle is all dissolved, and is then introduced into an intermittent industry
In microwave reaction kettle, 5 DEG C are cooled to, 33 kilograms of n-butanals and 20 kilograms of concentrated hydrochloric acids, the uniform simultaneously low-temp reaction 5 of mechanical agitation is added
The microwave generator being arranged in reaction kettle outer wall is opened after minute, microwave frequency is 1 × 109Hertz, microwave power 10 watts ~
It is adjustable between 20000 watts, inside and outside Synchronous Heating is carried out to reactant using microwave irradiation and temperature controls, makes temperature of reaction system
60 DEG C are gradually risen to from 5 DEG C, microwave irradiation closes microwave generator after ten minutes, and a large amount of white particles productions are precipitated in reaction kettle
Object, then imported into washing kettle and washed repeatedly with deionized water 5 times, it is then introduced into 60 DEG C of drying hot-air drying, obtains PVB
Resin-oatmeal finished product.
Reaction result：The acetalizing degree of product polyvinyl butyral is 78.2%, hydroxyl value 18.5%, hydroxyl and molecular weight
It is evenly distributed, the aldolisation saving heating time than conventional synthesis PVB resin powder is more than 3 hours.
Embodiment 2
In stainless steel dissolution kettle, the PVA particles of 10 parts by weight are put into, the deionized water of 90 parts by weight is added and are heated to 95
DEG C, mechanical agitation forms PVA aqueous solutions after so that solid particle is all dissolved.Claimed at room temperature by PVA aqueous solutions, n-butanal using weightless
It is added continuously in a continuous-type microwave reaction tube with the dilute hydrochloric acid of 1M, the addition speed of PVA aqueous solutions is 600 Grams Per Seconds, just
The addition speed of butyraldehyde is 35 Grams Per Seconds, and the addition speed of dilute hydrochloric acid is 200 Grams Per Seconds, opens the microwave being arranged in reaction pipe outer wall
Generator, microwave frequency are 2 × 109Hertz, microwave power is 5 kilowatts, is carried out to the reactant being added continuously in reaction tube
Microwave irradiation is evenly heated, and continuously all imported into the materials such as white particles product in washing kettle, is washed repeatedly with deionized water
It washs 5 times, is then introduced into 60 DEG C of drying hot-air drying, obtains PVB resin powder finished product.
Reaction result：The acetalizing degree of product polyvinyl butyral is 82.1%, hydroxyl value 14.9%, hydroxyl and molecular weight
It is evenly distributed, the aldolisation saving heating time than conventional synthesis PVB resin powder is more than 3 hours.
Embodiment 3
In a stainless steel dissolution kettle, the polyvinyl acetate of 10 parts by weight is put into（PVAc）, the methanol of 90 parts by weight is added,
The PVAc methanol solutions that 10wt% is formed after mechanical agitation dissolving, are then added the hydrogen of the deionized water and 1 parts by weight of 10 parts by weight
Sodium oxide molybdena keeps the temperature 5 hours and carries out alcoholysis after being warming up to 50 DEG C.Then material is imported into a micro-tubular microwave reactor,
5 DEG C are cooled to, the concentrated hydrochloric acid of the n-butanal and 2 parts by weight of 3 parts by weight is added, mechanical agitation simultaneously open after five minutes by low-temp reaction
Microwave generator, microwave frequency is 1 × 109Hertz ~ 3 × 1011Hertz between it is adjustable, microwave power 100 watts ~ 20000 watts it
Between it is adjustable, reactant is evenly heated using microwave irradiation and temperature control, so that temperature of reaction system is gradually increasing from 5 DEG C
To 60 DEG C, microwave irradiation closes microwave generator after ten minutes, a large amount of white particles products is precipitated in reaction kettle, then imported into water
It washes in kettle and is washed repeatedly with deionized water 5 times, be then introduced into 60 DEG C of drying hot-air drying, obtain PVB resin powder finished product.
Reaction result：The acetalizing degree of product polyvinyl butyral is 79.2%, hydroxyl value 18.3%, hydroxyl and molecular weight
It is evenly distributed, the aldolisation saving heating time than conventional synthesis PVB resin powder is more than 3 hours.
The foregoing is merely illustrative of the preferred embodiments of the present invention, and not to limit the present invention, all the present invention's
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within spirit and principle.
Claims (10)
1. a kind of method that microwave radiation technology efficiently produces PVB resin powder, it is characterised in that：PVA solution, aldehyde, catalyst is being added
Reactor in occur aldolisation heating process in, used frequency be 3 × 108Hertz ~ 3 × 1011The microwave of hertz is made
For a kind of heat source.
2. according to claim 1, which is characterized in that PVA is polyvinyl acetate after alcoholysis, in solid polyethylene alcohol
It is a kind of.
3. according to claim 1, which is characterized in that in PVA solution solvent be in water, methanol, ethyl alcohol, isopropanol at least
It is a kind of.
4. according to claim 1, aldehyde is at least one of butyraldehyde, n-butanal, isobutylaldehyde, and catalyst is hydrochloric acid, sulfuric acid, nitre
At least one of acid, phosphoric acid, sodium hydroxide, potassium hydroxide, sodium carbonate.
5. according to claim 1, reactor is added in PVA solution, aldehyde, catalyst mode is intermittent, continous way, semi continuous
In one kind.
6. according to claim 1, reactor is at least one of tank reactor, tubular reactor, micro-tubular reactor, micro-
Wave producer be set to inside reactor, outside reactor, reactor inside and outside have in one kind, the quantity of microwave generator
At least one.
7. according to claim 6, the microwave frequency of microwave generator is 3 × 108Hertz ~ 3 × 1011It is constant between hertz.
8. according to claim 6, the microwave frequency of microwave generator is 3 × 108Hertz ~ 3 × 1011It is adjustable between hertz.
9. according to claim 6, the microwave power of microwave generator is 1 watt ~ 1020It is constant between watt.
10. according to claim 6, the microwave power of microwave generator is 1 watt ~ 1020It is adjustable between watt.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810165417.1A CN108409897A (en) | 2018-02-28 | 2018-02-28 | A kind of method that microwave radiation technology efficiently produces PVB resin powder |
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| CN201810165417.1A CN108409897A (en) | 2018-02-28 | 2018-02-28 | A kind of method that microwave radiation technology efficiently produces PVB resin powder |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008188A (en) * | 2016-05-30 | 2016-10-12 | 浙江工业大学 | Novel method for preparing acraldehyde through glycerin catalytic dehydration |
| CN107446069A (en) * | 2017-07-21 | 2017-12-08 | 清华大学 | A kind of synthetic method of polyvinyl butyral resin |
| CN206897401U (en) * | 2017-06-16 | 2018-01-19 | 营口润达新材料有限公司 | Reactive modified phenolic resin kettle heater |
-
2018
- 2018-02-28 CN CN201810165417.1A patent/CN108409897A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008188A (en) * | 2016-05-30 | 2016-10-12 | 浙江工业大学 | Novel method for preparing acraldehyde through glycerin catalytic dehydration |
| CN206897401U (en) * | 2017-06-16 | 2018-01-19 | 营口润达新材料有限公司 | Reactive modified phenolic resin kettle heater |
| CN107446069A (en) * | 2017-07-21 | 2017-12-08 | 清华大学 | A kind of synthetic method of polyvinyl butyral resin |
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Application publication date: 20180817 |
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