CN108148156B - Polyvinyl butyral-based modified polymer and application thereof - Google Patents

Polyvinyl butyral-based modified polymer and application thereof Download PDF

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CN108148156B
CN108148156B CN201711446370.8A CN201711446370A CN108148156B CN 108148156 B CN108148156 B CN 108148156B CN 201711446370 A CN201711446370 A CN 201711446370A CN 108148156 B CN108148156 B CN 108148156B
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modified polymer
polyvinyl butyral
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CN108148156A (en
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傅冠颖
陈支勇
国星
黄嵚甫
蔡卫鹏
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Shanghai Centaur Enterprise Development Group Co.,Ltd.
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Jisheng Photoelectric Shenzhen Co ltd
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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
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
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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
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    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect
    • G02F2001/164—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on an electrochromic effect the electrolyte is made of polymers

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Abstract

The invention discloses a modified polymer based on polyvinyl butyral, which comprises a structural unit A, B, C, wherein the structural unit C is also connected with-O (CH)2CH2O)mR3Or- (Si-O)nR4. The structural units can be arranged and combined in sequence or in random, a regularly and repeatedly arranged polymer or a block copolymer or a random copolymerization polymer is formed, the obtained PVB-based novel polymer has excellent substrate binding power, the modified polymer is added with functional groups on the basis of PVB, has more proper thermal expansion rate and lower glass transfer temperature, has high conductivity and good low-temperature resistance when used as an electrolyte, can be applied to a low-temperature environment, meets special requirements, can well absorb the electrolyte, and has good application potential when used as the electrolyte in an electrochromic device.

Description

Polyvinyl butyral-based modified polymer and application thereof
Technical Field
The invention belongs to the technical field of electrochromic materials, relates to a novel polymer and application thereof, and particularly relates to a polyvinyl butyral based modified polymer and application thereof.
Background
The electrochromic is a phenomenon that the light absorption or light scattering characteristics of a substance change under the induction of an external voltage, and accordingly, a material which can change color under the action of an external electric field and current is an electrochromic material, the appearance of the material shows reversible changes of color and transparency, and a device made of the electrochromic material is an electrochromic device. The working principle of the electrochromic device is as follows: the electrochromic material generates electrochemical oxidation-reduction reaction under the action of an external electric field, so that electrons are lost, and the color of the material is changed. The electrochromic device generally comprises glass or a transparent substrate material, a transparent conducting layer (such as ITO), an electrochromic layer, an electrolyte layer, an ion storage layer, a transparent conducting layer (such as ITO), glass or a transparent substrate material which are sequentially arranged, and is expected to replace liquid crystal display due to the fact that the electrochromic device is free of visual angle display limitation, rich in color and short in response time, and can be widely applied to the fields of intelligent electrochromic glass, goggles, color-changing windows of buildings, sensors, analysis and the like.
The electrolyte layer is an important component of the electrochromic device and is made of a special conductive material, and polyvinyl butyral (PVB) has many excellent properties which are often used for polymer electrolytes, such as good light transmittance and ultraviolet radiation resistance, strong adhesion to glass, and is widely used for laminated glass in the fields of automobile glass and buildings. In the use, can make the PVB material into the film to it bonds glass to place it between two glass, when glass received external force and strikeed, the PVB film had shared partial impact energy, alleviateed glass's impaired degree, and when glass was cracked, the good adhesion force of PVB film made the glass piece be unlikely to scatter all around and splash, had promoted glass panel's security by a wide margin. In addition, PVB also has high transmittance and good adhesion to the electrodes, making it more suitable for use in polymer electrolytes.
The synthesis of PVB is started from vinyl acetate, after the vinyl acetate is synthesized into polyvinyl acetate through free radical, carboxyl of the polyvinyl acetate is converted into hydroxyl through strong base or alcohol to obtain polyvinyl alcohol (PVA), then the PVA and n-butyl aldehyde are subjected to acetalization reaction to prepare polyvinyl butyral, PVB with different hydroxyl ratios can be obtained according to different reaction degrees, generally speaking, the molecular structure of a PVB product has a structural unit with hydroxyl, and the mass fraction of the structural unit is 10-30%. However, the conventional PVB products in the market at present have properties that are not sufficient to meet some specific requirements, and have poor adhesion, thermal expansion rate and glass transition temperature, so that the PVB products are difficult to apply to low-temperature environments, and have low ionic conductivity, which limits the applications.
Disclosure of Invention
Therefore, the present invention is to solve the above technical problems, and to provide a modified polyvinyl butyral polymer with improved properties, which can meet the requirements of specific applications, and applications thereof.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention provides a modified polymer based on polyvinyl butyral, which comprises a structural unit A, B, C, wherein the structural unit A is
Figure 919533DEST_PATH_IMAGE001
The structural unit B is
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The structural unit C is
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The modified polymer has at least 1 structural unit A, B, C and the structural unit C is connected with-O (CH)2CH2O)mR3Or- (Si-O)nR4。
Preferably, R is1Is alkyl or is H; the R is2Is alkyl or is alkylene or is-O-or is H; the R is1When it is alkyl, said R1Is C1-C18An alkyl group or an alkyl group having a substituent E or an alkyl group having a substituent D inserted in the middle; the R is2When it is alkyl, said R2Is C1-C18An alkyl group or an alkyl group having a substituent E or an alkyl group having a substituent D inserted in the middle; the R is2Is alkyleneWhen R is equal to2is-CH2-、-CH2CH2CH（CN）-、-CH2CH2OCH2CH2-、-CH2CH2SCH2-、-CH2CH2NH2、-CH2CH2CHCl-、-CH2CH2CH（SO3H）-、-CH2CH2COOCH2-one of the above; the R is3Is C atom number 1-3 alkyl, the R4Is H or-SiR20R21R22。
Preferably, the substituent E is-OH, -OR, -CN, -COOH, -COOR, -SH, -SR, -NH2、-NR10H、-NR10R11、=CR10、=CR10R11、-SO3H. -CHO or halogen.
Preferably, the substituents D are-CO-, -COO-, -S-, -O-, -NR-, -SiR10R11or-CR10=CR11-。
Preferably, the R, R10、R11Are all C1-C8Alkyl or C6-C18Aryl radicals or by C1-C18Alkyl-substituted aryl radicals or C having-O-, -S-insertions1-C18An alkyl group.
Preferably, R is20、R21、R22Are all H or C1-C6An alkyl group.
Preferably, structural units A, B, C in the polymer are randomly arranged or ordered, wherein the ordered arrangement is at least one of a repeating arrangement or a block arrangement.
Preferably, m and n are each any integer between 1 and 12.
Preferably, R2When it is alkylene, the group-O (CH)2CH2O)mR3Or- (Si-O)nR4Is connected to R2；R2When it is H, the radical-O (CH)2CH2O)mR3Or- (Si-O)nR4Is linked to R2Connection ofC of (1).
The invention also provides application of the polyvinyl butyral based modified polymer in the field of electrochromism.
Compared with the prior art, the technical scheme of the invention has the following advantages:
the modified polymer based on polyvinyl butyral comprises a structural unit A, B, C, wherein the structural unit A is
Figure 828080DEST_PATH_IMAGE001
The structural unit B is
Figure 719813DEST_PATH_IMAGE002
The structural unit C is
Figure 123243DEST_PATH_IMAGE003
Said structural unit C is further connected with-O (CH)2CH2O)mR3Or- (Si-O)nR4。
The structural units can be arranged and combined in sequence or in random, a regularly and repeatedly arranged polymer or a block copolymer or a random copolymerization polymer is formed, the obtained PVB-based novel polymer has excellent substrate binding power, the modified polymer is added with functional groups on the basis of PVB, has more proper thermal expansion rate and lower glass transfer temperature, has high conductivity and good low-temperature resistance when used as an electrolyte, can be applied to a low-temperature environment, meets special requirements, can well absorb the electrolyte, and has good application potential when used as the electrolyte in an electrochromic device.
Detailed Description
In order that the present disclosure may be more readily and clearly understood, reference will now be made in detail to the present disclosure as illustrated in the accompanying drawings.
Example 1
This example provides a polyvinyl butyral based modifying polymer that includes structural element A, B, C, where structural element A is
Figure 24203DEST_PATH_IMAGE001
The structural unit B is
Figure 445957DEST_PATH_IMAGE002
The structural unit C is
Figure 321640DEST_PATH_IMAGE003
Said structural unit C is further connected with-O (CH)2CH2O)mR3In this example, R1Is n-propyl, R2is-CH2，R3is-CH3And m = 2. The modified polymer is connected by structural units A, B, C according to a regular repeating arrangement or a random arrangement, and the regular repeating arrangement is connected in a form of (ACCB) (ACCB) (ACCB) … … or a block arrangement, such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in the embodiment, O (CH)2CH2O)mR3Is connected to R2。
The structural general formula of the modified polymer is shown in the specification, wherein a, b and c are respectively a =0.35(a + b) -0.75 (a + b), b =0.25(a + b) -0.65 (a + b), and c/b = 0.1-1.
The present example also provides a process for preparing a polyvinyl butyral based modified polymer, comprising the steps of:
s1, tetrahydrofuran dehydration treatment: heating a double-mouth flask by using an electric heating bag, connecting one mouth of the flask with a condensation pipe with a flow measuring pipe, connecting an opening at the top of the condensation pipe with a nitrogen circulating pipe, keeping the device to be free of water vapor, adding tetrahydrofuran into the flask, adding a proper amount of metal sodium sheets and benzophenone, reacting sodium with water in the tetrahydrofuran to remove the water in the tetrahydrofuran, removing the water in the tetrahydrofuran to obtain purple benzophenone, and collecting the heated and condensed tetrahydrofuran.
S2, dissolving 3.61g of diethylene glycol monomethyl ether in 82ml of tetrahydrofuran obtained in the step S1, dissolving 2.1g of sodium hydride in 8ml of tetrahydrofuran, uniformly mixing and standing the two obtained solutions until no bubbles are generated, dropwise adding 10.9g of bromopropylene into the mixed solution, discharging heat in the mixed solution and generating hydrogen bromide gas in the reaction process, continuing stirring for 24 hours after reacting for 1-2 hours, diluting the mixed solution with ethyl acetate of the same volume, removing solids in the solution, and removing solvents tetrahydrofuran and ethyl acetate in the solution by reduced pressure distillation to obtain a pre-reaction solution.
S3, removing a stabilizer from vinyl acetate by an alkaline alumina column, dissolving 25g of vinyl acetate in 75ml of absolute ethanol, dissolving 50mg of Azodiisobutyronitrile (AIBN) in 5ml of absolute ethanol, mixing the ethanol filling liquid of the vinyl acetate with the pre-reaction liquid, placing the mixture in a double-mouth flask, connecting one port of the double-mouth flask with a return pipe, introducing nitrogen, heating the mixed solution to 70 ℃, adding an AIBN ethanol solution to react for 3 hours to obtain a light yellow precipitate, filtering the precipitate, washing with water and drying to obtain the modified polyvinyl acetate.
S4, preparing anhydrous potassium hydroxide saturated ethanol solution, filtering undissolved potassium hydroxide, dissolving 10g of modified polyvinyl acetate in the potassium hydroxide saturated ethanol solution, reacting at 50 ℃ for 6 hours to obtain precipitated modified polyvinyl alcohol, washing the modified polyvinyl alcohol with anhydrous ethanol until the modified polyvinyl alcohol is no longer alkaline, and drying for later use.
S5, dissolving 6g of modified polyvinyl alcohol and 1.6g of n-butanol in 100ml of 1M aqueous hydrogen chloride solution, transferring the solution into a flask, connecting a bottle mouth with a reflux pipe, reacting at 50 ℃ for 3 hours to obtain a white solid, and filtering to obtain the modified polyvinyl butyral:
Figure 461635DEST_PATH_IMAGE001
where a = 210, b = 85, and c = 18 (approximate values).
The polyvinyl butyral based modified polymer described in this example was used as an electrolyte in the field of electrochromic technology.
Example 2
This example provides a modified polyvinyl butyral based polymerThe modified polymer comprises a structural unit A, B, C, and the structural unit A is
Figure 166286DEST_PATH_IMAGE001
The structural unit B is
Figure 708125DEST_PATH_IMAGE002
The structural unit C is
Figure 689463DEST_PATH_IMAGE003
The structural unit C is also connected with- (Si-O)nR4In this example, R1Is n-propyl, R2is-O-, R4is-Si (CH)3)3And n = 1. The modified polymer is linked by structural units A, B, C in a regular repeating arrangement, such As (ACCB) (ACCB) (ACCB) … … or in a block arrangement, such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in this example, - (Si-O)nR4Is connected to R2The structural general formula of the modified polymer is as follows:
Figure DEST_PATH_IMAGE005
where a, b, c are a =230, b =160, c =160 (approximate values), respectively.
The preparation process of the modified polymer described in this example is:
s1, 6.01g of dimethyldimethoxysilane is taken and dissolved in 100ml of ethanol at 10 ℃, 1.0g of sodium hydroxide is added into the mixture, the solution is returned to the normal temperature (25-30 ℃) after being uniformly stirred, the stirring is continued for 1h, the solvent is completely removed by reduced pressure distillation, and the sodium salt of the dimethyldimethoxysilane is left.
S2, dissolving the sodium salt obtained in the step S1 in 250ml of anhydrous tetrahydrofuran, dropwise adding 5.4g of trimethylchlorosilane while stirring, continuously stirring for reacting for 3 hours, completely removing the tetrahydrofuran by reduced pressure distillation to obtain oily liquid, fully extracting sodium chloride generated in the reaction by pure water, and drying for 24 hours at 110 ℃ to obtain a siloxane oily product.
S3, taking 5g of polyvinyl butyral (the mass percentage of the structural unit of the hydroxyl section is 18%, the molecular weight is 4 ten thousand), completely dissolving in 100ml of anhydrous tetrahydrofuran, adding 1.35g of the siloxane oily product obtained in the step S2, heating to 40 ℃, continuously stirring for 24 hours to completely react, pouring the solution into pure water after the reaction is finished to separate out a polymer, washing the polymer obtained by filtering with pure water, petroleum ether, n-hexane and pure water for several times in sequence, and drying at 110 ℃ for 24 hours to obtain the modified polymer.
Example 3
This example provides a modified polyvinyl butyral based polymer that includes structural element A, B, C, where structural element A is
Figure 926541DEST_PATH_IMAGE001
The structural unit B is
Figure 169303DEST_PATH_IMAGE002
The structural unit C is
Figure 300070DEST_PATH_IMAGE003
Said structural unit C is further connected with-O (CH)2CH2O)mR3In this example, R1Is C18 alkyl, R2Is H, R3is-CH3And m = 6. The modified polymer is connected by structural units A, B, C according to a regular repeating arrangement or a random arrangement, and the regular repeating arrangement is connected in a form of (ACCB) (ACCB) (ACCB) … … or a block arrangement, such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in the embodiment, O (CH)2CH2O)mR3Is connected to the connection R2The structural general formula of the modified polymer is (ACCB), wherein a = 200, b = 200, and C = 50 (approximate value).
Example 4
This example provides a modified polyvinyl butyral based polymer that includes structural element A, B, C, where structural element A is
Figure 970086DEST_PATH_IMAGE001
The structural unit B is
Figure 835405DEST_PATH_IMAGE002
The structural unit C is
Figure 413017DEST_PATH_IMAGE003
Said structural unit C is further connected with-O (CH)2CH2O)mR3In this example, R1Is n-hexyl, R2Is isoheptyl, R3is-CH2CH2CH3And m = 3. The modified polymer is connected by structural units A, B, C according to a regular repeating arrangement or a random arrangement, and the regular repeating arrangement is connected in a form of (ACCB) (ACCB) (ACCB) … … or a block arrangement, such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in the embodiment, O (CH)2CH2O)mR3Is connected to R2The structural formula of the modified polymer is (AAAA) (BBBB) (CCCC), wherein a = 500, b = 240, and c = 75 (approximate values).
Example 5
This example provides a modified polyvinyl butyral based polymer that includes structural element A, B, C, where structural element A is
Figure 929449DEST_PATH_IMAGE001
The structural unit B is
Figure 521098DEST_PATH_IMAGE002
The structural unit C is
Figure 857402DEST_PATH_IMAGE003
Said structural unit C is further connected with-O (CH)2CH2O)mR3In this example, R1is-CH2CH2OH，R2is-CH2CH2CHCN，R3is-CH2CH3And m = 4. The modified polymer is connected by structural units A, B, C according to a regular repeating arrangement or a random arrangement, and the regular repeating arrangement is connected in a form of (ACCB) (ACCB) (ACCB) … … or a block arrangement, such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in the embodiment, O (CH)2CH2O)mR3Attached to R2, the modified polymer has the general structural formula (ACB), wherein a = 450, b = 550, and c = 300 (approximate values).
Example 6
This example provides a modified polyvinyl butyral based polymer that includes structural element A, B, C, where structural element A is
Figure 441967DEST_PATH_IMAGE001
The structural unit B is
Figure 812905DEST_PATH_IMAGE002
The structural unit C is
Figure 369264DEST_PATH_IMAGE003
The structural unit C is also connected with- (Si-O)nR4In this example, R1is-CH2CH2CH2COOR，R2is-CH2CH2OCH2CH2-，R4is-SiR20R21R22And n = 12. Wherein R is n-butyl, R20Is methyl, R21Is ethyl, R22And H, the modified polymer is connected by the structural unit A, B, C according to a regular repeated arrangement or a random arrangement, and the connection form is (ACC)B) (ACCB) (ACCB) … … or a block arrangement such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in this example, - (Si-O)nR4Is connected to R2The structural general formula of the modified polymer is ACBABC, wherein a =600, b = 250 and c = 30 (approximate value).
Example 7
This example provides a modified polyvinyl butyral based polymer that includes structural element A, B, C, where structural element A is
Figure 192864DEST_PATH_IMAGE001
The structural unit B is
Figure 581120DEST_PATH_IMAGE002
The structural unit C is
Figure 557297DEST_PATH_IMAGE003
The structural unit C is also connected with- (Si-O)nR4In this example, R1is-CH2CH2CH-NR10R11CH3，R2is-CH2CH2SCH2-，R4is-SiR20R21R22And n = 6. Wherein R is10Is isoamyl, R11Is methyl, R20Is n-butyl, R21Is isopropyl, R22The modified polymer is methyl linked by structural units A, B, C in a regular repeating arrangement, such As (ACCB) (ACCB) (ACCB) … … or in a block arrangement, such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in this example, - (Si-O)nR4Is connected to R2The structural general formula of the modified polymer is AABBCCAA, wherein, a = 80, b = 120 and c = 80 (approximate value).
Example 8
This example provides a modified polyvinyl butyral based polymer that includes structural element A, B, C, where structural element A is
Figure 740017DEST_PATH_IMAGE001
The structural unit B is
Figure 50912DEST_PATH_IMAGE002
The structural unit C is
Figure 977280DEST_PATH_IMAGE003
Said structural unit C is further connected with-O (CH)2CH2O)mR3In this example, R1is-CH2CHNRCH2CH3，R2is-CH2CH2NH2，R3is-CH2CH3And m = 8. The modified polymer is linked by structural units A, B, C in a regular repeating arrangement, such As (ACCB) (ACCB) (ACCB) … … or in a block arrangement, such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in this example, - (Si-O)nR4Is connected to R2The structural general formula of the modified polymer is (ACBC) (ACBC), wherein a = 120, b = 150 and c = 80 (approximate value).
Example 9
This example provides a modified polyvinyl butyral based polymer that includes structural element A, B, C, where structural element A is
Figure 604701DEST_PATH_IMAGE001
The structural unit B is
Figure 223902DEST_PATH_IMAGE002
The structural unit C is
Figure 22093DEST_PATH_IMAGE003
The structural unit C is also connected with- (Si-O)nR4In this example, R1Is H, R2is-CH2CH2CHCl，R4is-SiR20R21R22And n = 7. Wherein R is20Is C2Alkyl of R21Is C5 alkyl, R22Is C6The modified polymer is linked by structural units A, B, C in a regular repeating arrangement or in a random arrangement, the regular repeating arrangement being linked in the form of (ACCB) (ACCB) (ACCB) … … or in a block arrangement, such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in this example, - (Si-O)nR4Is connected to R2The structural general formula of the modified polymer is ACBAC, wherein a = 750, b = 500 and c = 300 (approximate value).
Example 10
This example provides a modified polyvinyl butyral based polymer that includes structural element A, B, C, where structural element A is
Figure 237305DEST_PATH_IMAGE001
The structural unit B is
Figure 171763DEST_PATH_IMAGE002
The structural unit C is
Figure 961865DEST_PATH_IMAGE003
The structural unit C is also connected with- (Si-O)nR4In this example, R1is-CH2CH2C=CR10CH3，R2is-CH2CH2CH-SO3H，R4Is H, n = 12. Wherein R is10Is C12 aryl, and is linked by structural unit A, B, C in a regular repeating arrangement or random arrangement, and the regular repeating arrangement is linked in a form of (ACCB) (ACCB) (ACCB) … … or block arrangement, such as (AAA …) (BBB …) (CCC …), (CC …)C …) (AAA …) (CCC …) (BBB …), in this example, - (Si-O)nR4Is connected to R2The structural general formula of the modified polymer is ACBACBA, wherein a = 900, b = 300 and c = 450 (approximate value).
Example 11
This example provides a modified polyvinyl butyral based polymer that includes structural element A, B, C, where structural element A is
Figure 791893DEST_PATH_IMAGE001
The structural unit B is
Figure 60063DEST_PATH_IMAGE002
The structural unit C is
Figure 114607DEST_PATH_IMAGE003
Said structural unit C is further connected with-O (CH)2CH2O)mR3In this example, R1is-CH2CH2CH- SiR10R11CH3，R2is-CH2CH2COOCH2-，R3is-CH3And m = 10. Wherein R is10is-CH 2CH2OCH2CH3, R11The modified polymer is tolyl, linked by structural units A, B, C in a regular repeating arrangement, such As (ACCB) (ACCB) (ACCB) … …, or in a block arrangement, such as (AAA …) (BBB …) (CCC …), (CCC …) (AAA …) (CCC …) (BBB …), in this example, - (Si-O)nR4Is connected to R2The structural general formula of the modified polymer is AABBCCAA, wherein a = 500, b = 500 and c = 20 (approximate value).
Examples of the experiments
1. Conventional PVB and the modified PVB polymer described in example 1 were prepared as polymer electrolytes, respectively: respectively taking 1 mass part of PVB, the modified polymer, 0.1 mass part of lithium perchlorate, 1 mass part of propylene carbonate and 0.003 mass part of leveling agentDissolving the solvent in 5 parts by mass of ethanol, pouring the obtained mixed solution into a polytetrafluoroethylene tray, and drying the obtained membrane layer at 70 ℃ for 1 hour after the ethanol is volatilized to obtain the polymer electrolyte. The conductivity of a conventional PVB electrolyte was measured to be 1.39x10 at 25 ℃-5S/cm, conductivity of the modified PVB electrolyte is 2.12 x10-5S/cm. Therefore, the electrolyte prepared from the modified PVB polymer has greatly improved conductivity and better conductive effect.
2. The physical and chemical parameters of conventional PVB and modified PVB polymers were measured separately and the results are shown in table 1:
TABLE 1
Figure DEST_PATH_IMAGE007
The test results show that compared with the conventional PVB, the modified PVB polymer has higher molecular weight dispersity, lower glass transition temperature and higher ethanol solubility, still has high activity at lower temperature and better ionic conductivity, can be used as a high-quality electrolyte material, and meets the requirements of specific condition application.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (3)

1. Modified polymer based on polyvinyl butyral, characterized in that it comprises structural unit A, B, C, unit A being
Figure 184780DEST_PATH_IMAGE001
The structural unit B is
Figure 264732DEST_PATH_IMAGE002
The structural unit C is
Figure 618353DEST_PATH_IMAGE003
The modified polymer has at least 1 structural unit A, B, C and the structural unit C is connected with-O (CH)2CH2O)mR3Or- (Si-O)nR4(ii) a The R is1Is alkyl or is H; the R is2Is alkyl or is alkylene or is-O-or is H; the R is1When it is alkyl, said R1Is C1-C18An alkyl group or an alkyl group having a substituent E or an alkyl group having a substituent D inserted in the middle; the R is2When it is alkyl, said R2Is C1-C18An alkyl group or an alkyl group having a substituent E or an alkyl group having a substituent D inserted in the middle; the R is2When it is alkylene, said R2is-CH2-、-CH2CH2CH（CN）-、-CH2CH2OCH2CH2-、-CH2CH2SCH2-、-CH2CH2CHCl-、-CH2CH2CH（SO3H）-、-CH2CH2COOCH2-one of the above; the R is3Is C atom number 1-3 alkyl, the R4Is H or-SiR20R21R22(ii) a The substituent E is-OH, -OR, -CN, -COOH, -COOR, -SH, -SR, -NH2、-NR10H、-NR10R11、=CR10R11、-SO3H. -CHO or halogen; the substituent D is-CO-, -COO-, -S-, -O-, -NR-, -SiR10R11-or-CR10=CR11-; the R, R10、R11Are all C1-C8Alkyl or C6-C18Aryl radicals or by C1-C18Alkyl-substituted aryl radicals or C having-O-, -S-insertions1-C18An alkyl group; the R is20、R21、R22Are all H or C1-C6An alkyl group; m and n are each 1-12Any integer in between.
2. The polyvinyl butyral based modified polymer of claim 1, wherein R is R2When it is alkylene or-O-, the group-O (CH)2CH2O)mR3Or- (Si-O)nR4Is connected to R2；R2When it is H, the radical-O (CH)2CH2O)mR3Or- (Si-O)nR4Is linked to R2And C is connected.
3. Use of a polyvinyl butyral based modifying polymer as claimed in any of claims 1 to 2 in the field of electrochromism.
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