CN105061651B - A kind of modified polyvinylalcohol of melt-processable and preparation method and application - Google Patents
A kind of modified polyvinylalcohol of melt-processable and preparation method and application Download PDFInfo
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- CN105061651B CN105061651B CN201510496921.6A CN201510496921A CN105061651B CN 105061651 B CN105061651 B CN 105061651B CN 201510496921 A CN201510496921 A CN 201510496921A CN 105061651 B CN105061651 B CN 105061651B
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Abstract
A kind of modified polyvinylalcohol of melt-processable and preparation method and application, the modified polyvinylalcohol has following general structure：Wherein, R1For alkyl chain, R2For hydrogen atom or the alkyl chain of end group hydroxyl, x ＞ 1, y ＞ 1, z >=1, and x ＞ y ＞ z, melting temperature are 160~230 DEG C, 250 DEG C of decomposition temperature ＞.Present invention additionally comprises the preparation method of the modified polyvinylalcohol of melt-processable and application.The present invention can be greatly reduced the melting temperature of modified polyvinylalcohol, and heat decomposition temperature is improved.The present invention is raw materials used to be easy to get, and operation is simple, and mild condition is insensitive to oxygen, water, and product yield high, selectivity are good；Product easy purification, post processing are simple.
Description
Technical field
The present invention relates to a kind of modified polyvinylalcohol and preparation method and application, and in particular to a kind of melt-processable
Modified polyvinylalcohol and preparation method and application.
Background technology
Polyvinyl alcohol is as a kind of high molecular weight water soluble polymer, and its performance is between plastics and rubber, with very strong
Adhesive property, flexility, oil resistance, solvent resistance, gas barrier property, colloid protective value, anti-wear performance and
Specially treated water resistance having etc., is widely used in coating for paper, film, health care, adhesive, building, emulsifying agent
With the industry such as dispersant, with the very high industry degree of correlation and wide research and development application prospect.
Contain in polyvinyl alcohol molecule chain and intramolecular and intermolecular hydrogen bonding easily formed between substantial amounts of hydroxyl, adjacent hydroxyl groups,
And polyvinyl alcohol molecule chain is regular, crystallinity is high, makes it have very high melting temperature, fusing point is up to 220~230 DEG C, with dividing
Temperature close is solved, it is difficult to melt-processed be carried out, so as to limit its application.Therefore, it is excellent in order to play polyvinyl alcohol
Material potential, the processing method for realizing and improving polyvinyl alcohol melting is the new direction of polyvinyl alcohol industrial development.
At present, substantial amounts of report has been carried out to polyvinyl alcohol melt processing both at home and abroad, mainly by physics (altogether
Mixed, plasticising) or chemical (copolymerization) is modified weakens between polyvinyl alcohol molecule and intramolecular hydrogen bond, reduces the fusing point of polyvinyl alcohol,
Realize the melt-processed of polyvinyl alcohol.Wherein, physical modification is mainly combined by polyvinyl alcohol and small molecule plasticizer,
The fusing point of polyvinyl alcohol is reduced, improves mobility, appropriate auxiliary agent realizes the melt-processed of polyvinyl alcohol in addition.But plasticising
The easy moisture absorption of agent, high temperature easily migrates volatilization, and the problems such as plasticization effect is undesirable remains unchanged presence.For example CN201210136954.6 is disclosed
A kind of method for melt processing of polyvinyl alcohol composite material, passes through the compound system of reasonable selection small molecule plasticizer, adds
Appropriate amount of addition agent is successfully realized the shaping of polyvinyl alcohol thermoplastic processing, although can solve polyvinyl alcohol melt-processed problem, and
Improved processing characteristics, mechanical property, outward appearance of composite etc., but be due to the use of plasticizer and auxiliary agent, it is difficult to
Ensure the stability of modified polyvinylalcohol.Modification by copolymerization is to carry out copolymerization in poly- second by vinyl acetate monomer and other monomers
Enol strand introduces the weaker monomer of active force, changes the chemical constitution and regularity of the strand of polyvinyl alcohol, weakens and divide
Sub interior, intermolecular hydrogen bonding, reduces its fusing point, improves the thermoplastic processability of polyvinyl alcohol.But modification by copolymerization technique is more multiple
Miscellaneous, difficulty is larger, and the country only has experimental study, and industrialization is also not implemented.It is for example disclosed in CN201210036388.1 fusible
The modified polyvinylalcohol of processing, the modified polyvinylalcohol obtained using comonomer and the vinyl acetate copolymerization of long-chain base, is made
Its decomposition temperature and melting temperature differ more than 30 DEG C, obtain excellent processing characteristics, but entirely reaction controllability is poor.
US 026302B2 make the second of the vinyl monomer containing polyalcohol key or the polyalcohol key obtained by alcoholysis using polymerisation in solution
Alkenyl monomer and vinyl acetate copolymerization, the modified polyvinylalcohol containing polyol structure obtained through alcoholysis, but need and it
His polyalcohol, a small amount of plasticizer are carried out mixing and then carrying out melt-processed, and reaction is difficult to control to.Journal of Polymer
Science:Part A:Polymer Chemistry,Vol.47,1317–1326(2009):“Pyrene Functional
A kind of side being modified to polyvinyl alcohol Azide is reported in the texts of Poly (vinyl alcohol) by " Click " Chemistry " one
The method that use " click chemistry " modified polyvinylalcohol is reported in method, a text, but and be not used for improve polyvinyl alcohol melting add
Work performance.
So far, do not study and Azide polyvinyl alcohol and fatty alcohol containing alkynyl are carried out into click chemistry reacted to be used for
The polyvinyl alcohol of melt-processable is prepared to polyvinyl alcohol modification.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of product yield high, selectivity is good, be easily isolated purification
Modified polyvinylalcohol of melt-processable and preparation method and application.
The present invention solve its technical problem use technical scheme be, a kind of modified polyvinylalcohol of melt-processable, its
General structure is as follows：
Wherein, R1For alkyl chain, R2For hydrogen atom or the alkyl chain of end group hydroxyl, x>1,y>1, z >=1, and x>y>Z gathers
Right is 1700~2500, and alcoholysis degree is 97~99%.
Further, the melting temperature of the modified polyvinylalcohol is 160~200 DEG C, decomposition temperature>250℃.
The present invention further solve its technical problem use technical scheme be, a kind of modified poly ethylene of melt-processable
The preparation method of alcohol, comprises the following steps：
(1) polyvinyl alcohol is dissolved in deionized water, is cooled to room temperature after being completely dissolved, pours into methanol and be precipitated out,
It is dried in vacuo the polyvinyl alcohol decrystallized；
(2) count by molar, 0.1 part of polyvinyl alcohol that decrystallizes is swelled 90 in anhydrous pyridine at 90~110 DEG C~
150min, is cooled to 0 DEG C, adds the paratoluensulfonyl chloride of 0.1~0.5 times of equivalent, is warming up to 20~30 DEG C of 22~26h of reaction,
After reaction terminates, precipitation in organic solvent (preferably methanol) is poured into, filtering, vacuum drying obtains the poly- of paratoluensulfonyl chloride modification
Vinyl alcohol (PVA-Ts)；
(3) count by molar, the polyvinyl alcohol that 0.1 part of paratoluensulfonyl chloride is modified is dissolved in DMF
(DMF) 8~10 parts of Sodium azide (NaN, are added3), react 46~50 hours at 60~70 DEG C, after reaction terminates, pour into organic molten
Precipitate, be washed with deionized in agent (preferably ether), filter, vacuum drying obtains the polyvinyl alcohol (PVA-N of Azide3)；
(4) count by molar, the polyvinyl alcohol of 0.1 part of Azide is dissolved in dimethyl sulfoxide (DMSO), add relative to folded
Fatty alcohol modified dose containing alkynyl of 1.1 times of equivalents of nitrogen functional group, then adds urging relative to 1.8 times of equivalents of nitrine functional group
Agent is reacted 46~50 hours, after reaction terminates, and is poured into ether and is precipitated, vacuum drying, and the modification for producing melt-processable gathers
Vinyl alcohol.
Further, in step (1), the polyvinyl alcohol trade mark is PVA0599, PVA1788, in PVA1799 and PVA2499
It is any.
Further, in step (4), the fatty alcohol modified dose of general structure containing alkynyl is as follows：
R in formula1For alkyl chain, R2For hydrogen atom or the alkyl chain of end group hydroxyl, more preferably Isosorbide-5-Nitrae-butynediols, propine
Alcohol, any of butynol and pentyne alcohol modifying agent.
The present invention further solve its technical problem use technical scheme be, a kind of modified poly ethylene of melt-processable
Application of the alcohol in 3D printing material.
Compared with prior art, the present invention has following beneficial technique effect：
1st, the present invention is carried out directly being modified to polyvinyl alcohol, is passed through click chemistry using the characteristic of polyvinyl alcohol polyhydroxy
The side base for the triazole ring that hydroxyl is introduced on polyvinyl alcohol molecule chain is reacted, the melting temperature of modified polyvinylalcohol can be made significantly
Reduction, heat decomposition temperature is improved.
2nd, the modified polyvinylalcohol for preparing of the present invention can be used directly to carry out melt-processed, be not required to add any plasticizer and
Auxiliary agent.
3rd, the present invention is raw materials used is easy to get, and operation is simple, and mild condition is insensitive to oxygen, water, product yield high,
Selectivity is good；Product easy purification, post processing are simple.
Brief description of the drawings
Fig. 1 is modified polyvinylalcohol prepared by the embodiment of the present invention 1~3 and the PVA1799 that is not modified DSC comparison diagrams.
Embodiment
The present invention is further illustrated with reference to embodiment.
Raw material：The polyvinyl alcohol trade mark PVA1799 and PVA2499 produce for sinopec Sichuan vinylon plant；1,4- butine two
Alcohol, propilolic alcohol, butynol, West Asia reagent.
Embodiment 1
(1) 10g PVA1799 are dissolved in 150ml deionized waters, are cooled to room temperature, poured into methanol and precipitate, filtering is true
Sky is dried, the polyvinyl alcohol decrystallized.
(2) the 4.4g PVA1799 that decrystallize are weighed to be swelled 2 hours for 100 DEG C in 110ml anhydrous pyridines, 0 DEG C is cooled to, plus
Enter 5.72g paratoluensulfonyl chlorides, be warming up to room temperature reaction 24 hours, reaction is poured into methanol after terminating and precipitated, and filtering, vacuum is done
It is dry, obtain the polyvinyl alcohol (PVA-Ts) of paratoluensulfonyl chloride modification.
(3) PVA-Ts of preparation is dissolved in 352ml DMF, adds 3.9g NaN3, react 48 hours at 65 DEG C, reaction
After end, pour into ether and precipitate, be washed with deionized, be dried in vacuo, obtain the polyvinyl alcohol (PVA-N of Azide3)。
(4) 2.2g PVA-N are weighed3It is dissolved in 33ml DMSO, adds Isosorbide-5-Nitrae-butynediols 0.26g, be subsequently added 0.84g
Sodium ascorbate and 0.21g CuSO4·5H2The O aqueous solution, holding solution system is 55ml, is reacted 48 hours, after reaction terminates
Pour into ether and precipitate, filter, vacuum drying produces the modified polyvinylalcohol of melt-processable, product yield is 90%.
Embodiment 2
(1) by the molten 150ml deionized waters of 10gPVA1799, room temperature is cooled to, pours into methanol and precipitates, filtering vacuum is done
The dry polyvinyl alcohol decrystallized.
(2) the 4.4g PVA1799 that decrystallize are weighed to be swelled 2 hours for 100 DEG C in 110ml anhydrous pyridines, 0 DEG C is cooled to, plus
Enter 7.63g paratoluensulfonyl chlorides, be warming up to room temperature reaction 24 hours, reaction is poured into methanol after terminating and precipitated, and filtering, vacuum is done
It is dry, obtain the polyvinyl alcohol (PVA-Ts) of paratoluensulfonyl chloride modification.
(3) PVA-Ts of preparation is dissolved in 352ml DMF, adds 5.2g NaN3, react 48 hours at 65 DEG C, reaction
After end, pour into ether and precipitate, be washed with deionized, be dried in vacuo, obtain the polyvinyl alcohol (PVA-N of Azide3)。
(4) 2.2g PVA-N are weighed3It is dissolved in 33ml DMSO, adds Isosorbide-5-Nitrae-butynediols 0.4g, be subsequently added 1.26g
Sodium ascorbate and 0.32g CuSO4·5H2The O aqueous solution, holding solution system is 55ml, is reacted 48 hours, after reaction terminates
Pour into ether and precipitate, filter, vacuum drying produces the modified polyvinylalcohol of melt-processable, product yield is 90%.
Embodiment 3
(1) 10g PVA1799 are dissolved in 150ml deionized waters, are cooled to room temperature, poured into methanol and precipitate, filtering is true
Sky is dried, the polyvinyl alcohol decrystallized.
(2) the 4.4g PVA1799 that decrystallize are weighed to be swelled 2 hours for 100 DEG C in 110ml anhydrous pyridines, 0 DEG C is cooled to, plus
Enter 7.63g paratoluensulfonyl chlorides, be warming up to room temperature reaction 24 hours, reaction is poured into methanol after terminating and precipitated, and filtering, vacuum is done
It is dry, obtain the polyvinyl alcohol (PVA-Ts) of paratoluensulfonyl chloride modification.
(3) PVA-Ts of preparation is dissolved in 352ml DMF, adds 5.2g NaN3, react 48 hours at 65 DEG C, reaction
After end, pour into ether and precipitate, be washed with deionized, be dried in vacuo, obtain the polyvinyl alcohol (PVA-N of Azide3)。
(4) 2.2g PVA-N are weighed3It is dissolved in 33ml DMSO, adds propilolic alcohol 0.24g, be subsequently added 1.26g Vitamin Cs
Sour sodium and 0.32g CuSO4·5H2The O aqueous solution, holding solution system is 55ml, is reacted 48 hours, and reaction pours into second after terminating
Precipitate, filter in ether, vacuum drying produces the modified polyvinylalcohol of melt-processable, product yield is 90%.
According to the fusing point and decomposition temperature of modified polyvinylalcohol respectively in means of differential scanning calorimetry Q20 (TA, USA) and thermogravimetric point
Analyzer Q50 (TA, USA) is measured in a nitrogen atmosphere according to 10 DEG C/min of heating rate.
The fusing point for measuring the modified polyvinylalcohol of the preparation of embodiment 1 is 189 DEG C, as shown in figure 1, decomposition temperature is 315 DEG C.
The fusing point for measuring the modified polyvinylalcohol of the preparation of embodiment 2 is 184 DEG C, as shown in figure 1, decomposition temperature is 315 DEG C, measures implementation
The fusing point of modified polyvinylalcohol prepared by example 3 is 196 DEG C, as shown in Figure 1.Decomposition temperature is 311 DEG C.
As shown in Figure 1, the fusing point of modified polyvinyl alcohol is significantly reduced, so as to further demonstrate the introducing of modifying agent
The melt-processed of polyvinyl alcohol can be achieved.
Claims (9)
1. a kind of modified polyvinylalcohol of melt-processable, it is characterised in that its general structure is as follows：
Wherein, R1For alkyl chain, R2For hydrogen atom or the alkyl chain of end group hydroxyl, x>1,y>1, z >=1, and x>y>Z, the degree of polymerization
For 1700~2500, alcoholysis degree is 97~99%.
2. the modified polyvinylalcohol of melt-processable according to claim 1, it is characterised in that the modified polyvinylalcohol
Melting temperature be 160~200 DEG C, decomposition temperature>250℃.
3. a kind of preparation method of the modified polyvinylalcohol of melt-processable as claimed in claim 1 or 2, it is characterised in that
Comprise the following steps：
(1) polyvinyl alcohol is dissolved in deionized water, is cooled to room temperature after being completely dissolved, pours into methanol and be precipitated out, vacuum
It is dried to obtain the polyvinyl alcohol decrystallized；
(2) count by molar, 0.1 part of polyvinyl alcohol that decrystallizes be swelled 90~150min in anhydrous pyridine at 90~110 DEG C,
0 DEG C is cooled to, the paratoluensulfonyl chloride of 0.1~0.5 times of equivalent is added, 20~30 DEG C of 22~26h of reaction are warming up to, reaction terminates
Afterwards, pour into organic solvent and precipitate, filtering, vacuum drying obtains the polyvinyl alcohol of paratoluensulfonyl chloride modification；
(3) count by molar, the polyvinyl alcohol that 0.1 part of paratoluensulfonyl chloride is modified is dissolved in DMF, add 8
~10 parts of Sodium azides, react 46~50 hours at 60~70 DEG C, after reaction terminates, and pour into organic solvent and precipitate, use deionization
Water washing, filtering, vacuum drying obtains the polyvinyl alcohol of Azide；
(4) count by molar, the polyvinyl alcohol of 0.1 part of Azide is dissolved in dimethyl sulfoxide, add relative to nitrine functional group 1.1
Fatty alcohol modified dose containing alkynyl of times equivalent, then adds the catalyst reaction 46 relative to 1.8 times of equivalents of nitrine functional group
~50 hours, after reaction terminates, pour into ether and precipitate, vacuum drying produces the modified polyvinylalcohol of melt-processable.
4. the preparation method of the modified polyvinylalcohol of melt-processable according to claim 3, it is characterised in that step
(1) in, the polyvinyl alcohol trade mark is PVA0599, PVA1788, any of PVA1799 and PVA2499.
5. the preparation method of the modified polyvinylalcohol of melt-processable according to claim 3, it is characterised in that step
(2) in, the organic solvent is methanol.
6. the preparation method of the modified polyvinylalcohol of melt-processable according to claim 3, it is characterised in that step
(3) in, the organic solvent is ether.
7. the preparation method of the modified polyvinylalcohol of the melt-processable according to one of claim 3~6, its feature exists
In in step (4), the fatty alcohol modified dose of general structure containing alkynyl is as follows：
R in formula1For alkyl chain, R2For hydrogen atom or the alkyl chain of end group hydroxyl.
8. the preparation method of the modified polyvinylalcohol of melt-processable according to claim 7, it is characterised in that described to contain
Fatty alcohol modified dose of alkynyl is Isosorbide-5-Nitrae-butynediols, propilolic alcohol, any of butynol and pentyne alcohol.
9. application of the modified polyvinylalcohol of melt-processable according to claim 1 or 2 in 3D printing material.
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