CN104987637A - Lignin-based compound heat stabilizer and method for improving heat stability of polyvinyl alcohol - Google Patents
Lignin-based compound heat stabilizer and method for improving heat stability of polyvinyl alcohol Download PDFInfo
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- CN104987637A CN104987637A CN201510299323.XA CN201510299323A CN104987637A CN 104987637 A CN104987637 A CN 104987637A CN 201510299323 A CN201510299323 A CN 201510299323A CN 104987637 A CN104987637 A CN 104987637A
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- polyvinyl alcohol
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Abstract
The invention provides a lignin-based compound heat stabilizer and a method for improving heat stability of polyvinyl alcohol. The heat stabilizer is prepared from the following components through mixing under stirring: 20 to 50 wt% of industrial lignin and 50 to 80 wt% of a grafting product of industrial lignin and acrylic acid-series vinyl monomer. The method for improving heat stability of polyvinyl alcohol by using the compound heat stabilizer comprises the following steps: adding lignin-based compound heat stabilizer and 100 parts of polyvinyl alcohol 1799 into deionized water and heating the obtained mixture in a water bath kettle at 90 DEG C for 2 to 3 h until the polyvinyl alcohol 1799 is totally dissolved, wherein a mass ratio of the compound heat stabilizer to the polyvinyl alcohol 1799 is 0.01 to 0.1; and drying the obtained mixed solution and carrying out film forming so as to obtain modified polyvinyl alcohol. When used for modification of polyvinyl alcohol, the compound heat stabilizer provided by the invention can greatly increase initial decomposition temperature and maximum decomposition temperature of polyvinyl alcohol, so a new idea about thermoplastic processing of polyvinyl alcohol is provided.
Description
Technical field
The invention belongs to for containing great amount of hydroxy group and the agent of carboxylic group polymer thermostable and using thermo-stabilizer to realize significantly improving the technical field of the thermostability of polyvinyl alcohol, be specifically related to a kind of lignin-base compound heat stabilizer and improve polyvinyl alcohol thermostability method.
Background technology
Polyvinyl alcohol is as a kind of water-soluble high-molecular material, and it has good water-soluble, film-forming properties, cementability and barrier, thus is widely used in the fields such as fiber, film and gel.Polyvinyl alcohol has fully biodegradable and blood compatibility simultaneously, therefore also comes into one's own gradually preparing in degradable material and medical product.In addition, polyvinyl alcohol or a kind of macromolecular material prepared by Non oil-based route, thus in today that petroleum resources lack day by day, greatly develop polyvinyl alcohol industry and have even more important meaning.
The great amount of hydroxy group group that polyvinyl alcohol molecule chain contains makes its molecular chain very easily be formed in molecular chain and hydrogen bond between molecular chain, these hydrogen bonds have not only become a kind of polymkeric substance of partial crystallization, also cause the melt temperature of polyvinyl alcohol (226 DEG C) and decomposition temperature very close, make polyvinyl alcohol decomposition reaction will occur while melting, thus make the thermoplastic difficult processing of polyvinyl alcohol to realize.Existing PVA (PVOH) FILM and fiber mainly to carry out machine-shaping by solution method, as wet-spinning, and solution film forming etc.Polyvinyl alcohol based on solution machine-shaping method only can prepare on the one hand film, fiber or as helping, auxiliary material, on the other hand because solution method machine-shaping need experience the process such as dissolving and drying, thus there is the shortcomings such as range of application is narrow, complex process, cost are high, yield poorly.Thermoplastic processing is compared solution processing and is had that technique is simple, energy consumption is low, cost is low, the high obvious advantage of efficiency, adopt extrude, three-dimensional article that the thermoplastic working method such as injection moulding then can prepare polyvinyl alcohol, thus greatly widen the Application Areas of polyvinyl alcohol.Therefore, realize the thermoplastic processing of polyvinyl alcohol, new vitality will be injected for polyvinyl alcohol industry, bring huge economic benefit and social influence.
For improving polyvinyl alcohol thermoplastic processibility, at present usually through the segmental mobility, the reduction crystal region that add softening agent raising polyvinyl alcohol, thus reduce fusing point.Common plasticizers has glycerine, and ethylene glycol etc. containing polyhydric small molecule polyol or low-molecular-weight polyoxyethylene glycol, but exist the precipitation of softening agent and the problem such as plasticizing efficiency is low.For overcoming polyvinyl alcohol fusing point and decomposition temperature close to causing the extremely narrow difficult point of its process window, in theory also by improving polyvinyl alcohol decomposition temperature thus realizing its melt-processed.Regrettably, do not have correlative study to report at present, first passage of the present invention adds the thermostability that modification thermo-stabilizer improves polyvinyl alcohol, novelty provide an other brand-new thinking for the processing of polyvinyl alcohol thermoplastic.
Summary of the invention
For solving above-mentioned prior art Problems existing, the object of the present invention is to provide a kind of lignin-base compound heat stabilizer and improve polyvinyl alcohol thermostability method, by adding highly efficiency compositional thermo-stabilizer, the initial of polyvinyl alcohol and maximum decomposition temperature significantly can be improved, for the thermoplastic processing realizing polyvinyl alcohol provides brand-new thinking when consumption (massfraction) is lower.
For achieving the above object, technical scheme of the present invention is:
A kind of lignin-base compound heat stabilizer, this compound heat stabilizer is formed through being uniformly mixed by following component by weight percentage:
Organic heat stabilizers A 20-50%
Organic heat stabilizers B 50-80%;
Wherein, organic heat stabilizers A is industrial lignin; Organic heat stabilizers B is industrial lignin and acrylic acid series vinyl monomer-grafted product.
Further, described industrial lignin be calcium lignin sulphonate, alkali wood sodium, sodium sulfate xylogen any one.
Further, organic heat stabilizers B is industrial lignin: any one and acrylic acid series vinyl monomer-grafted product of calcium lignin sulphonate, alkali wood sodium, sodium sulfate xylogen.
Use the method that described compound heat stabilizer improves polyvinyl alcohol thermostability, the method comprises the steps:
1) prepared by organic heat stabilizers B: take 1-2 part HLS-Ca, 15-30 part deionized water and be added to successively in three-necked bottle, stirs and makes it dissolve.Three-necked bottle is moved in water-bath, be progressively warming up to temperature of reaction 50 DEG C and after logical nitrogen protection 30min, add the K of 0.1-0.5 part
2s
2o
8initiation grafting reacts, after its reaction 20-30min, add the Resorcinol of 0.1-0.5 part and termination reaction.
2) lignin-base compound heat stabilizer/polyvinyl alcohol mixing solution preparation: the polyvinyl alcohol 100 parts getting lignin-base compound heat stabilizer and alcoholysis degree 99% adds in deionization, 2-3 is little dissolves completely up to 1799 polyvinyl alcohol in 90 DEG C of heating to be placed in water-bath, and compound heat stabilizer and polyvinyl alcohol mass ratio are 0.01-0.1;
3) lignin-base compound heat stabilizer/composite membrane of polyvinyl alcohol preparation: lignin-base compound heat stabilizer/polyvinyl alcohol mixing solution is poured in tetrafluoroethylene culture dish into (diameter is 12.5cm, high 1.0cm), insert dry 16h in vacuum drying oven subsequently, obtain lignin-base compound heat stabilizer/composite membrane of polyvinyl alcohol.
Wherein the number of each material is weight part.
Relative to prior art, beneficial effect of the present invention is:
1, provided by the present invention is polyvinyl alcohol composite thermo-stabilizer, and from conventionally by adding softening agent, to reduce by 1799 polyvinyl alcohol fusing points significantly different to realize polyvinyl alcohol thermoplastic processing thought, thinking of the present invention is pioneering.
2, provided by the present invention be lignin-base compound heat stabilizer addition extremely low provided by the present invention be a kind of based on the compound heat stabilizer of natural polymer xylogen, it derives from pulping and paper-making waste liquid, therefore cheap and wide material sources.
3, provided by the present invention is that lignin-base compound heat stabilizer addition is extremely low, and massfraction only accounts for 0.01-0.1 just significantly can improve the initial of 1799 polyvinyl alcohol and maximum decomposition temperature.
Embodiment
Below in conjunction with embodiment, technical solution of the present invention is described in further detail:
1) number of following examples material used is weight part.2) DuPontSDTQ600 is adopted to measure the maximum heat decomposition temperature of blend film; The temperature when loss of 1799PVA massfraction is 5% is defined as temperature of initial decomposition.
Embodiment 1
Wiring solution-forming in 100 parts of deionized waters is dissolved in acrylic acid series vinyl monomer-grafted product first by the calcium lignin sulphonate of 0.5 part and 0.5 part, then the polyvinyl alcohol of 100 part 1799 being joined in above-mentioned solution, in 90 DEG C of water-baths, heating 2-3 little of dissolving completely.Mixing solutions after dissolving is poured in tetrafluoroethylene culture dish, leaves standstill and insert dry 16h in vacuum drying oven in a moment, obtain lignin-base compound heat stabilizer/composite membrane of polyvinyl alcohol.
The maximum heat decomposition temperature of the polyvinyl alcohol material of the plasticization and modification of gained is 267.13 DEG C, and temperature of initial decomposition is 254.2 DEG C.
Embodiment 2
First by the calcium lignin sulphonate of the calcium lignin sulphonate of 1.5 parts and 1.5 parts be dissolved in wiring solution-forming in 100 parts of deionized waters with acrylic acid series vinyl monomer-grafted product, then the polyvinyl alcohol of 100 part 1799 being joined in above-mentioned solution, in 90 DEG C of water-baths, heating 2-3 little of dissolving completely.Mixing solutions after dissolving is poured in tetrafluoroethylene culture dish, leaves standstill and insert dry 16h in vacuum drying oven in a moment, obtain lignin-base compound heat stabilizer/composite membrane of polyvinyl alcohol.
The maximum heat decomposition temperature of the polyvinyl alcohol material of the plasticization and modification of gained is 366.6 DEG C, and temperature of initial decomposition is 318.3 DEG C.
Embodiment 3
First by the calcium lignin sulphonate of the calcium lignin sulphonate of 2.5 parts and 2.5 parts be dissolved in wiring solution-forming in 100 parts of deionized waters with acrylic acid series vinyl monomer-grafted product, then the polyvinyl alcohol of 100 part 1799 being joined in above-mentioned solution, in 90 DEG C of water-baths, heating 2-3 little of dissolving completely.Mixing solutions after dissolving is poured in tetrafluoroethylene culture dish, leaves standstill and insert dry 16h in vacuum drying oven in a moment, obtain lignin-base compound heat stabilizer/composite membrane of polyvinyl alcohol.
The maximum heat decomposition temperature of the polyvinyl alcohol material of the plasticization and modification of gained is 366.1 DEG C, and temperature of initial decomposition is 309.9 DEG C.
Embodiment 4
First by the alkali of 1.5 parts wood sodium and 1.5 parts alkali wood sodium be dissolved in wiring solution-forming in 100 parts of deionized waters with acrylic acid series vinyl monomer-grafted product, then the polyvinyl alcohol of 100 part 1799 being joined in above-mentioned solution, in 90 DEG C of water-baths, heating 2-3 little of dissolving completely.Mixing solutions after dissolving is poured in tetrafluoroethylene culture dish, leaves standstill and insert dry 16h in vacuum drying oven in a moment, obtain lignin-base compound heat stabilizer/composite membrane of polyvinyl alcohol.
The maximum heat decomposition temperature of the polyvinyl alcohol material of the plasticization and modification of gained is 332.4 DEG C, and temperature of initial decomposition is 285.3 DEG C.
Embodiment 5
First by the sodium sulfate xylogen of the sodium sulfate xylogen of 1.5 parts and 1.5 parts be dissolved in wiring solution-forming in 100 parts of deionized waters with acrylic acid series vinyl monomer-grafted product, then the polyvinyl alcohol of 100 part 1799 being joined in above-mentioned solution, in 90 DEG C of water-baths, heating 2-3 little of dissolving completely.Mixing solutions after dissolving is poured in tetrafluoroethylene culture dish, leaves standstill and insert dry 16h in vacuum drying oven in a moment, obtain lignin-base compound heat stabilizer/composite membrane of polyvinyl alcohol.
The maximum heat decomposition temperature of the polyvinyl alcohol material of the plasticization and modification of gained is 341.6 DEG C, and temperature of initial decomposition is 280.7 DEG C.
Comparative example
The maximum heat decomposition temperature of pure 1799 polyvinyl alcohol material is 258.1 DEG C, and temperature of initial decomposition is 237.4 DEG C.
The above, be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, and any change of expecting without creative work or replacement, all should be encompassed within protection scope of the present invention.Therefore, the protection domain that protection scope of the present invention should limit with claims is as the criterion.
Claims (4)
1. a lignin-base compound heat stabilizer, is characterized in that, this compound heat stabilizer is formed through being uniformly mixed by following component by weight percentage:
Organic heat stabilizers A 20-50%
Organic heat stabilizers B 50-80%;
Wherein, organic heat stabilizers A is industrial lignin; Organic heat stabilizers B is industrial lignin and acrylic acid series vinyl monomer-grafted product.
2. lignin-base compound heat stabilizer according to claim 1, is characterized in that, described industrial lignin be calcium lignin sulphonate, alkali wood sodium, sodium sulfate xylogen any one.
3. lignin-base compound heat stabilizer according to claim 1 and 2, is characterized in that, organic heat stabilizers B is industrial lignin: any one and acrylic acid series vinyl monomer-grafted product of calcium lignin sulphonate, alkali wood sodium, sodium sulfate xylogen.
4. improve the method for polyvinyl alcohol thermostability by compound heat stabilizer according to claim 3, it is characterized in that, the method comprises the steps:
1) prepared by organic heat stabilizers B: take 1-2 part HLS-Ca, 15-30 part deionized water and be added to successively in three-necked bottle, stirs and makes it dissolve.Three-necked bottle is moved in water-bath, be progressively warming up to temperature of reaction 50 DEG C and after logical nitrogen protection 30min, add the K of 0.1-0.5 part
2s
2o
8initiation grafting reacts, after its reaction 20-30min, add the Resorcinol of 0.1-0.5 part and termination reaction;
2) lignin-base compound heat stabilizer/polyvinyl alcohol mixing solution preparation: the polyvinyl alcohol 100 parts getting lignin-base compound heat stabilizer and alcoholysis degree 99% adds in deionization, 2-3 is little dissolves completely up to 1799 polyvinyl alcohol in 90 DEG C of heating to be placed in water-bath, and compound heat stabilizer and polyvinyl alcohol mass ratio are 0.01-0.1;
3) lignin-base compound heat stabilizer/composite membrane of polyvinyl alcohol preparation: lignin-base compound heat stabilizer/polyvinyl alcohol mixing solution is poured in tetrafluoroethylene culture dish, insert dry 16h in vacuum drying oven subsequently, obtain lignin-base compound heat stabilizer/composite membrane of polyvinyl alcohol;
Wherein the number of each material is weight part.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164943A (en) * | 2017-12-27 | 2018-06-15 | 湖南师范大学 | modified polylactic acid material and preparation method thereof |
| EP3825359A1 (en) * | 2019-11-20 | 2021-05-26 | Vito NV | Stabilizer for polyether having at least one reactive silyl group |
| CN113980355A (en) * | 2021-11-24 | 2022-01-28 | 中胶永生东南亚乳胶制品股份有限公司 | Multifunctional rubber additive and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103467759A (en) * | 2013-07-17 | 2013-12-25 | 东北林业大学 | Preparation method of industrial alkali lignin/polyvinyl alcohol cross-linked thin film |
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- 2015-06-03 CN CN201510299323.XA patent/CN104987637A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103467759A (en) * | 2013-07-17 | 2013-12-25 | 东北林业大学 | Preparation method of industrial alkali lignin/polyvinyl alcohol cross-linked thin film |
Non-Patent Citations (2)
| Title |
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| 姜黎 等: "木质素磺酸钙/聚乙烯醇共混体系的结构与性能", 《高分子材料科学与工程》 * |
| 李忠正: "《禾草类纤维制浆造纸》", 31 March 2013, 中国轻工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164943A (en) * | 2017-12-27 | 2018-06-15 | 湖南师范大学 | modified polylactic acid material and preparation method thereof |
| EP3825359A1 (en) * | 2019-11-20 | 2021-05-26 | Vito NV | Stabilizer for polyether having at least one reactive silyl group |
| CN113980355A (en) * | 2021-11-24 | 2022-01-28 | 中胶永生东南亚乳胶制品股份有限公司 | Multifunctional rubber additive and preparation method thereof |
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