CN100497418C - Polyvinyl acetate grafted copolymer and its free radical/positive ion converting polymerization process - Google Patents
Polyvinyl acetate grafted copolymer and its free radical/positive ion converting polymerization process Download PDFInfo
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- CN100497418C CN100497418C CNB2006100813712A CN200610081371A CN100497418C CN 100497418 C CN100497418 C CN 100497418C CN B2006100813712 A CNB2006100813712 A CN B2006100813712A CN 200610081371 A CN200610081371 A CN 200610081371A CN 100497418 C CN100497418 C CN 100497418C
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Abstract
The present invention discloses one kind of polyvinyl acetate grafted copolymer and its free radical/positive ion converting polymerization process. The polyvinyl acetate grafted copolymer has side chain grafted to the main chain of polyvinyl acetate, and features that the side chain is styrene derivative, vinyl carbazole homopolymer or olefin monomer copolymer. The polyvinyl acetate grafted copolymer is prepared through a free radical/positive ion converting polymerization process, and the process can prepare the copolymer in only one step and control the structure of the copolymer effectively.
Description
Technical field
The present invention relates to graft copolymer and preparation method thereof, particularly relate to a kind of polyvinyl acetate graft copolymer and free radical/cation transformation polymerization thereof.
Background technology
Graft copolymer is a family macromolecule surfactant, can be widely used in the preparation and the modification of polymer composite.At present, the synthetic method cardinal principle of graftomer is to produce grafting site by various mechanism on polymer chain, according to grafting site and side chain producing method, grafting method following a few class is arranged roughly:
1) grow side chain: earlier at the intermediate formation active site of a certain macromolecular chain, another monomeric polymerization of this active site re-initiation and grow side chain.This method document has a lot of reports, for example cellulosic modification etc.In patent CN1107685C, by this method vinyl pyridine in grafting on the polyvinyl alcohol.
2) macromonomer copolymerization grafting: macromonomer is the oligopolymer that has double-key end group, and can form graftomer after the vinyl monomer copolymerization.
3) grafting side chain: if having active lateral group on some macromolecular main chains, another macromole has active end group, and both react with regard to side chain in the grafting.Utilizing active cationic polymerization synthesising graft copolymer is the exemplary of these class methods (Sadahito Aoshita et al., Polymer Journal, 33 (8), 610-616 (2001)).In patent JP2001019770-A, use this method with polystyrene graft to the polyvinyl acetate (PVA) of partial hydrolysis.
For the method that grows side chain, owing to adopt radiation or illumination and other initiator, the position of active site and quantity are all restive on macromolecular chain, therefore for the structure regulating relative difficult of graftomer.The method of macromonomer copolymerization has better control to the structure and the percentage of grafting of graftomer, but needs first synthetic macromolecule monomer, makes the synthetic of graftomer become complicated.And the present method of grafting side chain, because the initiator system of positive ion active polymerization system is only to a kind of or a class monomer is effective, therefore the monomer surface of using is restricted.
Summary of the invention
The purpose of this invention is to provide a kind of polyvinyl acetate graft copolymer and preparation method thereof.
Polyvinyl acetate graft copolymer provided by the present invention is to be grafted with side chain on the polyvinyl acetate (PVA) main chain, it is characterized in that: described side chain is the homopolymer of the vinylcarbazole of the styrene derivatives of formula I structure or formula II structure; Perhaps, described side chain is the multipolymer of at least a and vinyl monomer in the vinyl ether of the vinylcarbazole of styrene derivatives, formula II structure of formula I structure and formula III structure;
Wherein, R
1Be C
1-C
10Alkyl; R
2Be C
1-C
10Alkyl or haloalkyl.
Common, R
1For-CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH (CH
3)
2,-CH
2CH
2CH
2CH
3,-C (CH
3)
3Etc. the fat alkane base; R
2For-CH
3,-CH
2CH
3,-CH
2CH
2C
1,-CH
2CH
2CH
2CH
3,-C (CH
3)
3Etc. fat alkane base or haloalkane alkyl.
In graftomer of the present invention, also can contain the monomeric unit of the cyclohexene oxide of formula IV structure in its graft side chain.
In the present invention, vinyl monomer be can with the monomer of the monomer generation copolymerization of formula I, formula II and formula III, comprise vinylbenzene, esters of acrylic acid, methyl acrylic ester, vinyl acetate, maleic anhydride, vinyl cyanide etc.
At polyvinyl acetate graft copolymer of the present invention, the length of side chain is molecular weight 2 thousand-4 ten thousand; Side chain is 55-95% at the percentage of grafting of main chain.The molecular weight of polyvinyl acetate (PVA) main chain is 5 thousand-20 ten thousand.
The preparation method of polyvinyl acetate graft copolymer of the present invention, be with reaction monomers, the polyvinyl acetate (PVA) of partial hydrolysis, radical initiator and electron acceptor(EA) mix, under 50-100 ℃, carry out polymerization and graft reaction, obtain described polyvinyl acetate graft copolymer;
Wherein, described reaction monomers is the styrene derivatives of formula I structure or the vinylcarbazole of formula II structure; Perhaps, it is the hybrid reaction monomer that comprises component A and B component, component A is selected from least a in the vinyl ether of the compound of styrene derivatives, formula II structure of formula I structure and formula III structure, B component is a vinyl monomer, and described vinyl monomer comprises vinylbenzene, esters of acrylic acid, methyl acrylic ester, vinyl acetate, maleic anhydride, vinyl cyanide; The mol ratio of component A and B component is 1:0.2-1:2,
Described electron acceptor(EA) is the diphenyl iodnium compounds of formula V structure;
(formula V)
Wherein, R is C
1-C
10Alkyl or alkoxyl group, as-CH
3,-CH
2CH
3,-CH
2CH
2CH
2CH
3,-C (CH
3)
3Etc. the fat alkane base or-OCH
3Deng alkoxyl group; X is PF
6 -, BF
4 -, AsF
6 -, CF
3SO
3 -Deng.
In order to improve grafting efficiency, also be added with the cyclohexene oxide of formula IV structure in the hybrid reaction monomer, the mol ratio of described cyclohexene oxide and component A is 1:0.5-2:1.
In reaction process, the mol ratio of reaction monomers and polyvinyl acetate polymer structural unit is 1:0.02-1:2.The molecular weight of the polyvinyl acetate (PVA) of used partial hydrolysis is 5 thousand-20 ten thousand, and wherein the hydroxyl molar percentage is 2-30%.The time of polymerization and graft reaction is 2-20 hours.
The present invention is an initiator with the polyvinyl acetate (PVA) (PVAc-OH) of partial hydrolysis, in organic solvent, transform the polymeric method with free radical/cation, grafting monomer and PVAc-OH etc. is joined reactor together, the initiation reaction monomer is grafted to then on the polyvinyl acetate (PVA) of partial hydrolysis and obtains graftomer.Have following advantage:
1) is " single stage method ", is about to grafting monomer and PVAc-OH etc. and joins reactor together that one step obtained target product;
2) be the uniqueness of grafting monomer, as with the multipolymer of vinyl cyanide (AN) and vinyl ether etc. as grafts, all can not realize with radical living polymerization and positive ion living polymerization;
3) easy, the easy row of reaction, agents useful for same is commercially produced product, does not need the such severe condition of living polymerization;
4) be easier to the to achieve a butt joint regulation and control of a polymer architecture.
Description of drawings
Fig. 1 is a synthetic method synoptic diagram of the present invention;
Fig. 2 is No. 4 samples among the embodiment 1
1H NMR spectrum;
Fig. 3 is the schema of graftomer sepn process;
Fig. 4 is the structural representation of graftomer;
Fig. 5 is No. 3 sample P artC among the embodiment 1
1H NMR spectrum;
Fig. 6 is the schema of graftomer sepn process;
Fig. 7 is No. 3 sample P artC among the embodiment 2
1H NMR spectrum;
Fig. 8 is No. 4 sample P art C among the embodiment 3
1H NMR spectrum.
Embodiment
The present invention adopts the principle of grafting, use free radical/cation and transform the polymeric method, free radical in the radical polymerization process is changed into positive ion, realize the synthetic of graftomer with the active group generation coupling on the macromolecular chain then, its reaction synoptic diagram as shown in Figure 1.The present invention can accomplish that single stage method synthesizes graftomer, and the achieve a butt joint control of a polymer architecture of the regulation and control of active group on the macromolecular chain that can add by control.
In the present invention, the available reaction monomers can be that the polymeric monomer can take place to transform, suc as formula the styrene derivatives of I structure, the compound of formula II structure and the vinyl ether of formula III structure etc., wherein, the compound of the styrene derivatives of formula I structure, formula II structure can form grafted chain separately as reaction monomers; Also can with other vinyl monomer generation copolymerization, as the grafted chain of polymkeric substance; And the vinyl ether of formula III structure can not use as reaction monomers separately, need form copolymerization with other monomers, could be connected on the side group of main polymer chain as grafted chain.Here, comonomer can be a binary, also can form multi-component copolymers such as ternary, quaternary, is advisable but generally be controlled within the binary.When copolymerization, total mol ratio of first kind of component (the polymeric reaction monomers can take place to transform the vinyl ether of the compound of the styrene derivatives of formula I structure, formula II structure and formula III structure etc.) and second kind of component (other vinyl monomers) generally is controlled at 1:0.2-1:2 and is advisable.When the content of second kind of component is very few, to the regulating and controlling effect reduction of resulting polymers structure; During too high levels, be unfavorable for the formation of graft copolymer.Because, for present used electron acceptor(EA), the free radical of the vinyl ether of the compound of the styrene derivatives of formula I structure, formula II structure and formula III structure can only be converted into positive ion, therefore in the polymerization system, the monomeric content of this three class can not be low excessively, otherwise just can't transform polymerization smoothly.Usually, other vinyl monomers that can be used as second kind of component are vinylbenzene, esters of acrylic acid or methyl acrylic ester, vinyl acetate, maleic anhydride, vinyl cyanide etc.
When carrying out copolymerized grafting, also can in comonomer, add the compound of formula IV structure.This compound chain transfer constant is less, can carry out cationic polymerization under comparatively high temps, thereby improves grafting efficiency.The mol ratio of this compound and first kind of component is 1:0.5-2:1.
In reaction process of the present invention, electron acceptor(EA) is that reaction is necessary, wherein is preferably the diphenyl iodnium compounds of formula V structure.
(formula V)
Wherein, R is C
1-C
10Alkyl or alkoxyl group, as-CH
3,-CH
2CH
3,-CH
2CH
2CH
2CH
3,-C (CH
3)
3Etc. the fat alkane base or-OCH
3Deng alkoxyl group; X is PF
6 -, BF
4 -, AsF
6 -, CF
3SO
3 -Deng.Introduce aliphatic hydrocarbon on the phenyl ring and can improve the solvability of electron acceptor(EA) in organic solvent, and the introducing of alkoxyl group can improve the solvability and the ability of accepting electronics of electron acceptor(EA).
Radical initiator can be the initiator system that Raolical polymerizable is used always, and is the most frequently used as Diisopropyl azodicarboxylate (AIBN) etc.
As the polyvinyl acetate (PVA) of main chain, be applied in reaction system of the present invention before, need carry out partial hydrolysis to it, make it have activity hydroxy and be beneficial to take place graft reaction.Partial hydrolysis polyvinyl acetate (PVA) sample among the present invention adopts the mode of acidic hydrolysis to prepare, and the hydroxyl that this mode produces is randomly dispersed on the main chain, and hydrolysis rate is relatively slow, by the adjusting of acidity, is easy to the degree of hydrolysis of controlling polymers.The hydroxyl molar content of this sample generally is controlled at 2-30% scope, and when hydroxy radical content was too high, its solvability in organic solvent reduced, and is unfavorable for the carrying out of graft reaction.The molecular weight ranges of this sample is 5 thousand-20 ten thousand, and when molecular weight was too big, system viscosity was bigger, also is unfavorable for the carrying out that reacts.
Graft reaction condition of the present invention is fairly simple, be single stage method: with polyvinyl acetate (PVA), radical initiator and the electron acceptor(EA) of reaction monomers, partial hydrolysis, disposable joining in the polymerizing pipe, under common Raolical polymerizable temperature (50-100 ℃), reaction 2-20 hour gets final product a step to obtain described polyvinyl acetate graft copolymer.Because, in the monomeric radical polymerization process of branch body, coupled reaction with hydroxyl does not take place, after this growth free radical generates positive ion by the electron-transfer reaction to electron acceptor(EA), " on the spot " with the polyvinyl acetate (PVA) of partial hydrolysis in hydroxyl carry out coupled reaction, original position generates described graft copolymer.And common positive ion living polymerization legal system needs preparation earlier to have the branch body polymkeric substance of active end group when being equipped with graftomer, and adding the trunk body polymkeric substance that has active group then carries out coupled reaction, is two-step approach.
Below adopt specific embodiment, further describe the present invention.
Synthesizing of embodiment 1 MOS/CHO/PVAc-OH system graftomer
One, raw material
MOS:p-methoxy styrene (CH
2=CHC
6H
4OCH
3)
CHO: cyclohexene oxide (C
6H
10O)
AIBN: Diisopropyl azodicarboxylate, radical initiator
Ph
2IPF
6: diphenyl iodine hexafluorophosphate, electron acceptor(EA)
PVAc-OH: the polyvinyl acetate (PVA) of partial hydrolysis
(polymerization degree is 220, Mn=1.9 * 10
4, hydroxy radical content is 16%, Kuraray company)
Two, graft polymerization reaction
All monomers, radical initiator and electron acceptor(EA) are added in the polymerizing pipe according to ratio in the table 1, on the vacuum line with liquid nitrogen vacuum cycle back (or logical nitrogen is after the 10 minutes) tube sealing that repeatedly outgases, polymerization four hours under 80 ℃ temperature condition then.
The graft polymerization of table 1 MOS/CHO/PVAC-OH system
Polymerization time, 4 hours; Polymerization temperature, 80 ℃; Solvent, 1, the 2-ethylene dichloride; Precipitation agent, 1,2, No. 4 polymerizing pipe precipitates in methyl alcohol, and No. 3 polymerizing pipe precipitates in normal hexane, separates by Fig. 3.
In the table 1, be the radical polymerization of MOS (radical polymerization can not take place CHO) No. 1; No. 2 is the conversion polymerization of MOS/CHO, promptly in the MOS radical polymerization process, electronics of growth radical transfer is to electron acceptor(EA) Ph2IPF6, and self is transformed into positive ion, this positive ion causes CHO and carries out cationic polymerization, obtains the PMOS-b-PCHO segmented copolymer; No. 3 is the graft polymerization of MOS/CHO/PVAc-OH, promptly adds PVAc-OH in above-mentioned conversion polymerization system, and the positive ion end in an OH group wherein and the growth carries out coupled reaction, and obtaining PVAc is that main chain, PMOS-b-PCHO are the graft copolymer of side chain.No. 4 is the radical polymerization of the MOS in the presence of PVAc-OH.As can be seen from Table 1, No. 1 consistent with No. 4 output, and do not observe the signal of PVAc-OH in No. 4 the NMR spectrum, is MOS homopolymer (Fig. 2), illustrates that PVAc-OH can ignore the influence of the radical polymerization of MOS under this experiment condition.No. 2 polymer output increases greatly, its
1The bright PCHO structural unit that contains of H NMR stave illustrates the conversion polymerization from the free radical to the positive ion (referring to Haiqing Guo (Guo Haiqing) etc., Macromolecules, 1996,29,2354) has taken place.No. 3 polymer outputs increase than the output of No. 1 radical polymerization, contain PMOS in the polymkeric substance simultaneously, and the structural unit of PCHO and PVAc-OH illustrates graft polymerization has taken place.
By the listed flow process of Fig. 3 No. 3 polymkeric substance in the table 1 are separated:
No. 3 polymers solns in the table 1 are precipitated in normal hexane, and the PCHO homopolymer dissolves in normal hexane, stays in the liquid phase.Remove wherein solvent with Rotary Evaporators, resistates gets PartA with ethylene dichloride dissolving back precipitation, vacuum-drying in methyl alcohol.Precipitation precipitates in methyl alcohol after dissolving with THF, and is centrifugal under 3000 rev/mins low-speed centrifugal condition, to remove (the Part B) such as PMOS homopolymer on the insoluble PVAc-OH of not receiving in methyl alcohol.Because the main chain part PVAc-OH in the graftomer dissolves in methyl alcohol, pendant moiety PMOS-b-PCHO is insoluble to methyl alcohol, so graftomer is muddy state in methyl alcohol, but in methanol (volume ratio=5: 4) mixed solvent, can precipitate (Part C).And the free PVAc-OH of grafted does not dissolve in and (sees Table 2) in this mixed solvent, removes wherein solvent with Rotary Evaporators, and resistates gets Part D with ethylene dichloride dissolving back precipitation, vacuum-drying in normal hexane.Separation and NMR characterization result see Table 3, and Fig. 4 is seen in the graftomer structural representation.
Table 2 PVAc-OH is in the solvability of methyl alcohol and water mixed system
No. 3 graftomer separating resultings of table 3
As shown in Table 3, except PCHO, also contain a certain amount of PMOS structural unit among the Part A.Because PMOS can not dissolve in normal hexane, this part should be the PMOS structural unit that is connected on the CHO segment.Therefore Part A is the homopolymer of PCHO and the mixture of PMOS-b-PCHO segmented copolymer, and content accounts for 28.3% of total polymer amount.Part B content less (4.3%), and the grafts of composition and Part C is much at one.The amount that PMOS homopolymer in this part and PMOS-b-PCHO segmented copolymer are described can be ignored, and this part polymkeric substance also is a graftomer.This result and MOS/CHO transform in the polymerization system, do not have the result of PMOS homopolymer consistent (Haiqing Guo (Guo Haiqing) etc., Macromolecules, 1996,29,2354).Part D is free PVAc-OH.Part C is a graftomer, its
1H NMR composes as shown in Figure 5, and its weight accounts for 61%.The system percentage of grafting is 65%.
The calculating of percentage of grafting:
Polymkeric substance total amount * 100% that percentage of grafting=the be grafted to polymer/polymeric on the PVAc-OH generates wherein, polymkeric substance on the PVAc-OH of the polymkeric substance total amount that polymerization generates=be not grafted to+the be grafted to polymkeric substance on the PVAc-OH
The regulation and control that embodiment 2 MOS/CHO/PVAc-OH system graftomer are formed (adjusting the ratio of MOS/CHO and PVAc-OH)
All monomers, radical initiator and electron acceptor(EA) are added in the polymerizing pipe according to ratio in the table 4, on vacuum line with the liquid nitrogen vacuum cycle back tube sealing that repeatedly outgases, polymerization four hours under 80 ℃ temperature condition then.
Graft polymerization under the table 4 MOS/CHO/PVAC-OH system different ratios
Polymerization time, 4 hours; Polymerization temperature, 80 ℃; Solvent, 1, the 2-ethylene dichloride; Precipitation agent, normal hexane.
According to the result of table 3,, all be graftomer according to Part B and the Part C composition basically identical that the separation method of Fig. 3 obtains.Therefore, when the graftomer that obtains under each condition separates, removed the separating step of PartB from his-and-hers watches 4.Adopt the method for Fig. 6 to separate, the results are shown in Table 5 and table 6.
The separation and the sign of table 5 MOS/CHO/PVAC-OH system graftomer
The sign of table 6 MOS/CHO/PVAC-OH system graftomer
A:M is the total monomer mole number; PVAc-OH: be the molecular weight of the mole number=quality/VAc of polyvinyl acetate (PVA) structural unit.
As can be seen from Table 6, the unitary mol ratio of branched structure unit and backbone structure can be by regulating the control recently that feeds intake of side chain monomer and main chain PVAc-OH in the graftomer.Under above-mentioned experiment condition, the unitary mol ratio variation range of branched structure unit and backbone structure is 1:0.85-1:0.26, and the mol ratio of corresponding side chain monomer and main chain PVAc-OH structural unit is 1:0.26-1:0.05.The unitary mol ratio of branched structure unit and backbone structure can be regulated and control arbitrarily as required, generally is controlled at the scope of 1:0.02-1:2.
Synthesizing of embodiment 3 AN/BVE/CHO/PVAc-OH system graftomer
Raw material:
AN: vinyl cyanide (CH
2=CHCN)
BVE: vinyl-n-butyl ether (CH
2=CHOC
4H
9)
CHO: cyclohexene oxide (C
6H
10O)
AIBN: Diisopropyl azodicarboxylate, radical initiator
Ph
2IPF
6: diphenyl iodonium hexafluorophosphate, electron acceptor(EA)
PVAc-OH: the polyvinyl acetate (PVA) of partial hydrolysis
(polymerization degree is 220, Mn=1.9 * 10
4, hydroxy radical content is 16%, Kuraray company)
All monomers, radical initiator and electron acceptor(EA) are added in the homemade glass polymerizing pipe according to ratio in the table 7, the consumption that changes different PVAc-OH on vacuum line with the liquid nitrogen vacuum cycle back tube sealing that repeatedly outgases, polymerization 4 hours under 80 ℃ temperature condition then.
Synthesizing of graftomer under the table 7 PVAc-OH different amounts
Polymerization time, 4 hours; Polymerization temperature, 80 ℃; Solvent, 1, the 2-ethylene dichloride; Precipitation agent, 1,2, No. 3 polymerizing pipe methanol extraction, 4,5, No. 6 polymerizing pipe precipitates with normal hexane, and separates according to the separation method of Fig. 3.
In the table 7, No. 1 is the radical polymerization of AN/BVE/CHO system, and No. 2 is the conversion polymerization of AN/BVE/CHO system, No. 3 radical polymerization for the AN/BVE/CHO system under the PVAc-OH existence; 4,5, No. 6 is the graft polymerization of AN/BVE/CHO/PVAc-OH system.
Contrast the output of No. 1 and No. 3, in the error allowed band, can think both output basically identical, fail to observe the signal of PVAc-OH simultaneously in No. 3 the NMR spectrum (Fig. 7), therefore can think for this system, under this experiment condition, PVAc-OH can ignore the radical polymerization influence of AN/BVE/CHO.4,5, No. 6 characterization results see Table 8 and table 9.
The sign of table 8 AN/BVE/CHO/PVAc-OH system graftomer
The sign of table 9 AN/BVE/CHO/PVAc-OH system graftomer
A:M is the total monomer mole number; PVAc-OH: be the molecular weight of the mole number=quality/VAc of polyvinyl acetate (PVA) structural unit.
As can be seen from Table 9, similar with the MOS/CHO/PVAC-OH system, branched structure unit and the unitary mol ratio of backbone structure also can be by regulating the control recently that feeds intake of monomer and PVAc-OH in the AN/BVE/CHO/PVAc-OH system gained graftomer.Under above-mentioned experiment condition, the unitary mol ratio variation range of branched structure unit and backbone structure is 1:0.21-1:0.42.The mol ratio of corresponding monomer and PVAc-OH structural unit is 1:0.11-1:0.14.The unitary mol ratio of branched structure unit and backbone structure can be regulated and control arbitrarily as required, generally is controlled at the scope of 1:0.02-1:2.And the percentage of grafting of this system is than the percentage of grafting height of MOS/CHO/PVAC-OH system.
The solvability of embodiment 4, polymkeric substance
Different polymkeric substance are dissolved with different solvents, and the result is as shown in table 10.
The solvability of table 10 polymkeric substance
A: the graftomer of two individual system (MOS/CHO/PVAc-OH, AN/BVE/CHO/PVAc-OH two systems)
According to the solvability of table 10, as can be seen, the PVAc-OH of main chain can be dissolved in the methyl alcohol, and the side chain segment is undissolved in methyl alcohol, therefore makes graftomer can stable dispersion become white emulsion in methyl alcohol.
Claims (8)
1, a kind of polyvinyl acetate graft copolymer, be on the polyvinyl acetate (PVA) main chain, to be grafted with side chain, it is characterized in that: described side chain is the homopolymer of the styrene derivatives of formula I structure, or the styrene derivatives of formula I structure and the multipolymer of vinyl monomer;
Wherein, R
1Be C
1-C
10Alkyl;
Described vinyl monomer is vinylbenzene, esters of acrylic acid, methyl acrylic ester, vinyl acetate, maleic anhydride or vinyl cyanide; The mol ratio of described styrene derivatives and described vinyl monomer is 1:0.2-1:2.
2, polyvinyl acetate graft copolymer according to claim 1 is characterized in that: R
1For-CH
3,-CH
2CH
3,-CH
2CH
2CH
3,-CH (CH
3)
2,-CH
2CH
2CH
2CH
3Or-C (CH
3)
3
3, polyvinyl acetate graft copolymer according to claim 1 and 2 is characterized in that: the molecular weight of described side chain is 2 thousand-4 ten thousand; Described side chain is 55-95% at the percentage of grafting of main chain; The molecular weight of described polyvinyl acetate (PVA) main chain is 5 thousand-20 ten thousand.
4, polyvinyl acetate graft copolymer according to claim 1 is characterized in that: the monomeric unit that also contains the cyclohexene oxide of formula IV structure in the described side chain
5, the preparation method of the described polyvinyl acetate graft copolymer of claim 1, be with reaction monomers, the polyvinyl acetate (PVA) of partial hydrolysis, radical initiator and electron acceptor(EA) mix, under 50-100 ℃, carry out polymerization and graft reaction, obtain described polyvinyl acetate graft copolymer;
Wherein, described reaction monomers is the styrene derivatives of formula I structure; Perhaps, be the hybrid reaction monomer of component A and B component, component A is the styrene derivatives of formula I structure, and B component is a vinyl monomer, and described vinyl monomer is vinylbenzene, esters of acrylic acid, methyl acrylic ester, vinyl acetate, maleic anhydride or vinyl cyanide; The mol ratio of component A and B component is 1:0.2-1:2,
Described electron acceptor(EA) is the diphenyl iodnium compounds of formula V structure;
(formula V)
Wherein, R is C
1-C
10Alkyl or alkoxyl group; X is PF
6 -, BF
4 -, AsF
6 -Or CF
3SO
3 -
6, preparation method according to claim 5 is characterized in that: the mol ratio of described reaction monomers and polyvinyl acetate polymer structural unit is 1:0.02-1:2.
7, according to claim 5 or 6 described preparation methods, it is characterized in that: the molecular weight of the polyvinyl acetate (PVA) of described partial hydrolysis is 5 thousand-20 ten thousand, and wherein the hydroxyl molar percentage is 2-30%.
8, according to claim 5 or 6 described preparation methods, it is characterized in that: the time of polyreaction is 2-20 hours.
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| 自由基/正离子转化聚合法合成对甲氧基苯乙烯与环己烯氧化物/1，2，5，6-二环氧基环辛烷的嵌段共聚物. 郭海清，方震等.高分子学报，第5期. 2002 |
| 自由基/正离子转化聚合法合成对甲氧基苯乙烯与环己烯氧化物/1，2，5，6-二环氧基环辛烷的嵌段共聚物. 郭海清，方震等.高分子学报，第5期. 2002 * |
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