CN107602919B - The method that the modified hollow glass microbead of the method for modifying and gained of hollow glass microbead is used to prepare starch or composite membrane of polyvinyl alcohol - Google Patents
The method that the modified hollow glass microbead of the method for modifying and gained of hollow glass microbead is used to prepare starch or composite membrane of polyvinyl alcohol Download PDFInfo
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Abstract
The present invention provides the methods that a kind of method of modifying of hollow glass microbead and the modified hollow glass microbead of gained are used to prepare starch or composite membrane of polyvinyl alcohol, it is related to that hollow glass microbead is processing modified and biodegradable composite film technical field, the method of modifying of the hollow glass microbead, including the surface of hollow glass microbead is contacted with chloroacetic acid solution, obtain the step of monoxone is modified hollow glass microbead, the technical issues of application of this method alleviates hollow glass microbead in the prior art and polyvinyl alcohol or starch poor compatibility, reach can hold well with biodegradation materials such as starch or polyvinyl alcohol and technical effect.
Description
Technical field
The present invention relates to hollow glass microbead is processing modified and biodegradable composite film technical field, more particularly, to one kind
The modified hollow glass microbead of the method for modifying and gained of hollow glass microbead is used to prepare the side of starch or composite membrane of polyvinyl alcohol
Method.
Background technique
Plastics are especially important one in the invention of great significance for change human lives.Plastics have penetrated into each of human lives
A aspect, it and steel, timber, cement become four big stay materials side by side.Plastics are also brought while bringing civilization
Some harm, disposable plastic waste, such as: plastic film, refuse bag, shopping bag, tableware, food packaging and industrial packaging
The environmental problem of material etc., the initiations such as polluted agricultural land, seashore harbour and tourist attraction is got worse, and causes the very big of the whole society
Concern and strong repercussion.Exploitation degradation plastic is the important channel for alleviating " white pollution ".In numerous alternative degradations
In material, polyvinyl alcohol (PVA) is obtained by the aggregated alcoholysis of vinylacetate, is the modeling of current commercialization biological degradability
Generally the least expensive material in material；And the cheap, from a wealth of sources of starch, regeneration period are short, it is considered to be most with prospects
One of biodegradation material.And it is lower, resistance to explain membrane material intensity using polyvinyl alcohol or starch as the biology that base-material is made merely
Heat, acid-proof alkaline are poor, are unable to satisfy requirement.
Hollow glass microbead is mainly borosilicate in chemical component, is a kind of hollow glass that micron-sized surface is smooth
Glass microballoon.Glassy state plus hollow structure assign its have different from other materials or hollow body unique performance, such as it is light,
The performances such as heat-resisting, acidproof aqueous slkali, low thermally conductive, sound insulation, electrical isolation.Have with the compound material of hollow glass microbead and significantly mentions
High mechanical strength mitigates weight and heat insulation and preservation effect.And the materials such as hollow glass microbead and vinyl alcohol plastics or starch
It carries out when blending prepares composite material that its compatibility is poor, causes the intensity of composite material lower, and completely with biodegrade
Material is matrix, and the composite material containing hollow glass microbead not yet appears in the newspapers.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of method of modifying of hollow glass microbead, in the prior art to alleviate
The technical issues of hollow glass microbead and polyvinyl alcohol or starch poor compatibility, the hollow glass of modification being prepared using this method
Glass microballon and polyvinyl alcohol or starch have good compatibility.
The second object of the present invention is to provide the preparation method of a kind of starch composite membrane or composite membrane of polyvinyl alcohol, benefit
The starch composite membrane or composite membrane of polyvinyl alcohol prepared with this method have excellent mechanical property under the premise of degradable.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of method of modifying of hollow glass microbead, including the surface of hollow glass microbead is contacted with chloroacetic acid solution,
The step of monoxone is modified hollow glass microbead is obtained, optionally, further includes:
The solid mixture obtained after the modified hollow glass microbead of monoxone is mixed with starch is placed in molten including water, ammonium hydroxide
It is reacted in liquid and the mixed solution of hydrazine hydrate solution, obtains starch conversion hollow glass microbead；
Or,
The solid mixture obtained after the modified hollow glass microbead of monoxone and polyvinyl alcohol is placed in including water, ammonia
It is reacted in aqueous solution and the mixed solution of hydrazine hydrate solution, obtains polyvinyl alcohol modification hollow glass microbead.
Compared with the prior art, the invention has the following beneficial effects:
The present invention is by being surface-treated hollow glass microbead with monoxone, to introduce on hollow glass microbead surface
Carboxylic acid group, so as to so that carboxylic acid group on the hydroxyl and hollow glass microbead of starch or polyvinyl alcohol forms covalent bond,
To increase the bonding strength of hollow glass microbead and starch or polyvinyl alcohol.Modified hollow glass microbead, hydrophily
Be improved, it is preferable with the compatibility of film, can hold well with biodegradation materials such as starch or polyvinyl alcohol and, to mention
The mechanical property of high biodegradation material and the moisture-vapor transmission of composite membrane, improve the service performance of Biodegradable films.
The starch conversion hollow glass microbead or polyvinyl alcohol modification that the preparation method provided through the invention obtains are hollow
Glass microballoon mixes the compatibility that can be further improved the two using starch conversion hollow glass microbead, to mention with starch
The bond strength of high starch and hollow glass microbead；It can be with using polyvinyl alcohol modification hollow glass microbead and polyvinyl alcohol
The compatibility for further increasing the two, to improve the bond strength of polyvinyl alcohol and hollow glass microbead.
Further, the solid mixture obtained after the modified hollow glass microbead of monoxone being mixed with starch be placed in including
It is reacted in water, ammonia spirit and the mixed solution of hydrazine hydrate solution, the hollow glass of starch conversion is obtained after filtering and drying
Glass microballon；
Or,
The solid mixture obtained after the modified hollow glass microbead of monoxone and polyvinyl alcohol is placed in including water, ammonia
It is reacted in aqueous solution and the mixed solution of hydrazine hydrate solution, polyvinyl alcohol modification hollow glass is obtained after filtering and drying
Microballon.
Further, the surface by hollow glass microbead is contacted with chloroacetic acid solution the following steps are included: by hollow
Glass microballoon, which is placed in chloroacetic acid solution, to be reacted, and it is micro- that the modified hollow glass of monoxone is obtained after then washed and dry
Pearl.
Further, the mass fraction of the chloroacetic acid solution is 0.1-5%, and chloroacetic acid solution is typical but non-limiting
Mass fraction is for example are as follows: 0.1%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5% or 5%.
Further, the hollow glass microbead is placed in reaction condition when being reacted in chloroacetic acid solution are as follows: in 0-
0.5-2h is reacted under the conditions of 60 DEG C.Item is reacted by limit chloroacetic concentration and hollow glass microbead and the chloroacetic acid solution
Part further can effectively control hollow glass microbead and react with chloroacetic, make the carboxylic acid group on hollow glass microbead surface
More evenly.
Wherein, hollow glass microbead and temperature when chloroacetate reaction are unrestricted for example are as follows: 0 DEG C, 5 DEG C, 10 DEG C, 15
DEG C, 20 DEG C, 25 DEG C, 30 DEG C, 35 DEG C, 40 DEG C, 45 DEG C, 50 DEG C, 55 DEG C or 60 DEG C；The unrestricted reaction time is for example are as follows:
0.5h, 1h, 1.5h or 2h.
It further, further include having to hollow before washing after the hollow glass microbead is reacted with the chloroacetic acid solution
The operation that the mixture of glass microballoon and chloroacetic acid solution is filtered；Optionally, the drying is vacuum drying.
Further, again by the surface of hollow glass microbead and chloroethene after being cleaned with aqueous slkali to hollow glass microbead
Acid solution contact.Hollow glass microbead is handled with aqueous slkali, the hydrophily of hollow glass microbead can be further increased,
It is contacted with reinforcing hollow glass microbead with chloroacetic surface.
Further, hollow glass microbead is cleaned with aqueous slkali, comprising the following steps: by hollow glass microbead with
Aqueous slkali mixing, ultrasonic mixing handle 0.1-2h, then flow back under the conditions of 50-90 DEG C of oil bath, mechanical stirring 0.1-2h.
Wherein, the typical but non-limiting ultrasonic mixing time is for example are as follows: 0.1h, 0.5h, 1h, 1.5h or 2h；It is unrestricted
The oil bath reflux temperature of property is, for example, 50 DEG C, 55 DEG C, 60 DEG C, 65 DEG C, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C or 90 DEG C；It is non-limiting
The mechanical stirring time for example are as follows: 0.1h, 0.5h, 1h, 1.5h or 2h.
Further, the mass fraction of the aqueous slkali is 0.5-5%；Optionally, the aqueous slkali includes sodium hydroxide
One of solution, potassium hydroxide solution, sodium carbonate liquor or solution of potassium carbonate or at least two combination；Optionally, water, ammonia
The volume ratio of aqueous solution and hydrazine hydrate solution is 100:(5-20): 1, preferably 100:(5-15): 1, further preferably 100:
10:1；Optionally, the mass fraction of the ammonia spirit is 20%-30%；Optionally, the mass fraction of the hydrazine hydrate solution
For 75-85%；Optionally, the mass ratio of the mixed solution and the solid mixture is (5-20): 1, preferably (5-15):
1, further preferably 10:1；Optionally, the step of solid mixture is reacted in the mixed solution includes: institute
It states after solid mixture is placed in the mixed solution and first stirs 20-40min, then react 3-5h at 70-100 DEG C.
Wherein, the typical but non-limiting volume ratio of water, ammonia spirit and hydrazine hydrate solution is 100:5:1,100:10:
1,100:15:1 or 100:20:1.The typical but non-limiting mass fraction of ammonia spirit is, for example, 20%, 22%, 25%,
27% or 30%.The typical but non-limiting mass fraction of hydrazine hydrate solution is, for example, 75%, 77%, 80%, 83% or 85%.
Mixing liquid and the typical but non-limiting mass ratio of solid mixture are 5:1,15:1,10:1 or 20:1.Solid mixture with
Typical but non-limiting temperature is, for example, 70 DEG C, 75 DEG C, 80 DEG C, 85 DEG C, 90 DEG C, 85 DEG C or 90 DEG C when mixing liquid reaction,
The typical but non-limiting time is, for example, 3h, 3.5h, 4h, 4.5h or 5h.
A kind of modified hollow glass microbead, including monoxone is prepared according to the method for modifying of above-mentioned hollow glass microbead
Modified hollow glass microbead or starch conversion hollow glass microbead or polyvinyl alcohol modification hollow glass microbead.Above-mentioned monoxone changes
Property hollow glass microbead or starch conversion hollow glass microbead or polyvinyl alcohol modification hollow glass microbead can be with starch or poly-
Vinyl alcohol preferably hold and.
A kind of preparation method of starch composite membrane, comprising the following steps: the modification of glycerol, starch and above-mentioned monoxone is hollow
Glass microballoon or the mixing of starch conversion hollow glass microbead, obtain the starch composite membrane after extrusion and compacting.
Starch composite membrane provided by the invention is prepared using fusion method, using biodegradation material starch as base-material, wherein
After adding the modified hollow glass microbead of monoxone or starch conversion hollow glass microbead, the mechanical property of starch composite membrane can be improved
Energy and moisture-vapor transmission make it more need to can completely actually use demand.
Hydroxyl in glycerol can form interaction of hydrogen bond with starch hydroxyl, and glycerol can increase the flexible of starch film
Property；Glycerol is very few, and starch film becomes fragile；Glycerol is excessive, and starch film-strength is deteriorated.
Further, comprising the following steps: first glycerol and starch are mixed, add the modified hollow glass microbead of monoxone
Or starch conversion hollow glass microbead, the starch composite membrane is obtained after extrusion and compacting；Optionally, mixing used when mixing
The revolving speed of machine is 2500-4000r/min；Optionally, the mass ratio of the glycerol and the starch is (0.1-0.5): 1, preferably
For (0.2-0.4): 1, further preferably 0.3:1；Optionally, the modified hollow glass microbead of the monoxone of addition or starch conversion
The quality of hollow glass microbead accounts for the 1-20% of the starch quality.Control the modified hollow glass microbead of monoxone or starch conversion
The additional amount of hollow glass microbead can prevent that influence starch compound because agglomeration occurs for modified hollow glass microbead itself
The performance of film.
Wherein, the matter of the modified hollow glass microbead of typical but non-limiting monoxone or starch conversion hollow glass microbead
Amount accounts for 1%, 2%, 5%, 8%, 10%, 12%, 15%, 17% or the 20% of the starch quality.
A kind of preparation method of composite membrane of polyvinyl alcohol, comprising the following steps: by polyvinyl alcohol, glycerol and above-mentioned monoxone
Modified hollow glass microbead or polyvinyl alcohol modification hollow glass microbead are dissolved in hot water, and poly- second is dried to obtain after stirring evenly
Enol composite membrane.Composite membrane of polyvinyl alcohol provided by the invention is prepared using solwution method, is with biodegradation material polyvinyl alcohol
Base-material can improve poly- after adding the modified hollow glass microbead of monoxone or polyvinyl alcohol modification hollow glass microbead wherein
The mechanical property and moisture-vapor transmission of vinyl alcohol composite membrane make it more need to can completely actually use demand.The wherein temperature of hot water
It is 60-90 DEG C.
Hydroxyl in glycerol can form interaction of hydrogen bond with polyvinyl alcohol hydroxyl, and glycerol can increase polyvinyl alcohol film
Flexibility；Glycerol is very few, and starch film becomes fragile；Glycerol is excessive, and polyvinyl alcohol film-strength is deteriorated.
Further, comprising the following steps: first by polyvinyl alcohol be added hot water in, after polyvinyl alcohol dissolution completely after again according to
It is secondary that glycerol and the modified hollow glass microbead of monoxone or polyvinyl alcohol modification hollow glass microbead, stirring to chlorine are added into solution
The modified hollow glass microbead of acetic acid or polyvinyl alcohol modification hollow glass microbead stop heating after being uniformly dispersed, and acquired solution is fallen
Enter in mold and be dried, the composite membrane of polyvinyl alcohol is obtained after demoulding.
Further, the mass concentration of polyvinyl alcohol is 1-10% in the solution that polyvinyl alcohol obtains after being added in hot water.
The mass concentration of typical but non-limiting polyvinyl alcohol is, for example, 1%, 2%, 5%, 8% or 10%.
Further, the glycerol is the 1-30% of polyvinyl alcohol weight；Optionally, the modified hollow glass of the monoxone
Microballon or polyvinyl alcohol modification hollow glass microbead are the 1-20% of polyvinyl alcohol weight；Optionally, drying temperature is when dry
50-80 DEG C, drying time 2-5h.Control the modified hollow glass microbead of monoxone or polyvinyl alcohol modification hollow glass microbead
Additional amount can prevent that the performance for influencing composite membrane of polyvinyl alcohol due to reunion occurs because of modified hollow glass microbead itself.
In above-mentioned preferred embodiment, the modified hollow glass microbead of typical but non-limiting monoxone or polyethylene
The quality of the modified hollow glass microbead of alcohol account for the starch quality 1%, 2%, 5%, 8%, 10%, 12%, 15%, 17% or
20%.
Specific embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
The conventional products that can be obtained by commercially available purchase.
Below in conjunction with embodiment and comparative example, the present invention will be further described in detail.
Embodiment 1
A kind of modified hollow glass microbead of monoxone, is prepared by the following method to obtain:
25g hollow glass microbead is mixed with the chloroacetic acid solution of 250mL 1%, in 40 DEG C of reaction 2h, is then taken out
Filter operation, later washs hollow glass microbead with distilled water, until it is neutral, it is vacuum dried at 60 DEG C, obtain chloroethene
The modified hollow glass microbead of acid.
Embodiment 2
A kind of modified hollow glass microbead of monoxone, is prepared by the following method to obtain:
25g hollow glass microbead is mixed with the sodium hydroxide solution of 250mL 2%, ultrasonic mixing handles 1h, then exists
90 DEG C of reflux mechanical stirring 1h under the conditions of oil bath after having reacted, are added 2.5g monoxone in 40 DEG C of reaction 2h, are then filtered
Operation, later washs hollow glass microbead with distilled water, until it is neutral, it is vacuum dried at 60 DEG C, obtain monoxone
Modified hollow glass microbead.
Embodiment 3
A kind of starch conversion hollow glass microbead, is prepared by the following method to obtain:
The hydrazine hydrate solution of 2.5L water, 250mL 25wt% ammonia spirit and 25mL 80wt% is mixed, configuration mixing
Solution；500g mixed solution is taken, the modified hollow glass microbead of the monoxone being added in 25g embodiment 1 and 25g starch, stirring
In 90 DEG C of reaction 4h after 30min, starch conversion hollow glass microbead is obtained after filtering and drying.
Embodiment 4
A kind of starch conversion hollow glass microbead, is prepared by the following method to obtain:
The hydrazine hydrate solution of 2.5L water, 250mL 25wt% ammonia spirit and 25mL 80wt% is mixed, configuration mixing
Solution；500g mixed solution is taken, the modified hollow glass microbead of the monoxone being added in 25g embodiment 2 and 25g starch, stirring
In 90 DEG C of reaction 4h after 30min, starch conversion hollow glass microbead is obtained after filtering and drying.
Embodiment 5
A kind of polyvinyl alcohol modification hollow glass microbead, is prepared by the following method to obtain:
The hydrazine hydrate solution of 2.5L water, the ammonia spirit of 250mL 25wt% and 25mL 80wt% is mixed, configuration is mixed
Close solution；500g mixed solution is taken, the modified hollow glass microbead of the monoxone being added in 25g embodiment 2 and 25g polyvinyl alcohol,
In 90 DEG C of reaction 4h after stirring 30min, polyvinyl alcohol modification hollow glass microbead is obtained.
Embodiment 6
A kind of starch composite membrane is prepared by the following method to obtain:
Glycerol, starch are added in high-speed mixer by weight the ratio of 0.3:1 and are mixed, is added in embodiment 2 and obtains
The modified hollow glass microbead of the monoxone arrived, weight are the 10% of starch weight, and screw rod plastic extruder squeezes out, the mixing
Extrusion temperature of the object from feed inlet to head is followed successively by 120 DEG C~140 DEG C~140 DEG C, obtains bar, uses vulcanizing press
120 DEG C of compacting film forming, obtain starch composite membrane.
Embodiment 7
A kind of starch composite membrane, preparation method is same as Example 6, the difference is that, monoxone in embodiment 6 is changed
The 20% of the Change Weight To starch weight of property hollow glass microbead, other conditions are constant.
Embodiment 8
A kind of starch composite membrane is prepared by the following method to obtain:
Glycerol, starch are added in high-speed mixer by weight the ratio of 0.3:1 and are mixed, is added in embodiment 3 and obtains
The starch conversion hollow glass microbead arrived, weight are the 10% of starch weight, and screw rod plastic extruder squeezes out, the mixture
Extrusion temperature from feed inlet to head is followed successively by 120 DEG C~140 DEG C~140 DEG C, obtains bar, with vulcanizing press 120
DEG C compacting film forming, obtain starch composite membrane.
Embodiment 9
A kind of starch composite membrane, preparation method is same as Example 8, the difference is that, it will form sediment obtained in embodiment 3
The modified hollow glass microbead of powder is changed to starch conversion hollow glass microbead obtained in embodiment 4, and other conditions are constant.
Embodiment 10
A kind of starch composite membrane, preparation method is same as Example 9, the difference is that, by starch conversion in embodiment 9
The 20% of the Change Weight To starch weight of hollow glass microbead, other conditions are constant.
Embodiment 11
A kind of composite membrane of polyvinyl alcohol is prepared by the following method to obtain:
It dissolves polyvinyl alcohol in 80 DEG C of hot water, polyvinyl alcohol weight 5%, 30% weight of polyvinyl alcohol is added
The modified hollow glass microbead of monoxone obtained in embodiment 2 is added in above-mentioned solution by glycerol, the modified hollow glass of monoxone
The weight of glass microballon is the 10% of polyvinyl alcohol weight, is continued after stirring is uniformly dispersed to the modified hollow glass microbead of monoxone,
Stop heating, pours into mold, it is 4 hours dry at 60 DEG C, obtain composite membrane of polyvinyl alcohol.
Embodiment 12
A kind of composite membrane of polyvinyl alcohol, preparation method is identical as embodiment 11, the difference is that, by chlorine in embodiment 11
The 20% of the Change Weight To polyvinyl alcohol weight of the modified hollow glass microbead of acetic acid, other conditions are constant.
Embodiment 13
A kind of composite membrane of polyvinyl alcohol is prepared by the following method to obtain:
It dissolves polyvinyl alcohol in 80 DEG C of hot water, polyvinyl alcohol weight 5%, 30% weight of polyvinyl alcohol is added
Polyvinyl alcohol modification hollow glass microbead obtained in embodiment 5 is added in above-mentioned solution, in polyvinyl alcohol modification by glycerol
The weight of empty glass microballoon be polyvinyl alcohol weight 10%, continue stirring be uniformly dispersed to hollow glass microbead after, stop plus
Heat is poured into mold, 4 hours dry at 60 DEG C, obtains composite membrane of polyvinyl alcohol.
Embodiment 14
A kind of composite membrane of polyvinyl alcohol, preparation method is identical as embodiment 13, the difference is that, it will gather in embodiment 13
The 20% of the Change Weight To polyvinyl alcohol weight of modified vinyl alcohol hollow glass microbead, other conditions are constant.
Comparative example 1
A kind of modified hollow glass microbead, is prepared by the following method to obtain:
25g hollow glass microbead is mixed with the sodium hydroxide solution of 250mL 2%, ultrasonic mixing handles 1h, then exists
90 DEG C of reflux mechanical stirring 1h, after having reacted, are filtered, are washed with distilled water to hollow glass microbead, directly under the conditions of oil bath
It to neutrality, is then dried in vacuo through 60 DEG C, obtains the modified hollow glass microbead of sodium hydroxide.
Comparative example 2
A kind of starch composite membrane is prepared by the following method to obtain:
Glycerol, starch are added in high-speed mixer by weight the ratio of 0.3:1 and are mixed, unmodified hollow glass is added
Glass microballon, weight are the 10% of starch weight, and screw rod plastic extruder squeezes out, the mixture squeezing from feed inlet to head
Temperature is followed successively by 120 DEG C~140 DEG C~140 DEG C out, obtains bar, with 120 DEG C of compacting film forming of vulcanizing press, obtains starch
Composite membrane.
Comparative example 3
A kind of starch composite membrane, preparation method is identical as comparative example 2, the difference is that, in unmodified in comparative example 2
The 20% of the Change Weight To starch weight of empty glass microballoon, other conditions are constant.
Comparative example 4
A kind of starch composite membrane, preparation method is identical as comparative example 2, the difference is that, in unmodified in comparative example 2
Empty glass microballoon is changed to the modified hollow glass microbead of sodium hydroxide obtained in comparative example 1, and other conditions are constant.
Comparative example 5
A kind of starch composite membrane, preparation method is identical as comparative example 4, the difference is that, by sodium hydroxide in comparative example 4
The 20% of the Change Weight To starch weight of modified hollow glass microbead, other conditions are constant.
Comparative example 6
The present embodiment is a kind of thermoplastic starch film, is prepared only with starch.Specific method includes by glycerol, starch
It is added in high-speed mixer and mixes by weight the ratio of 0.3:1, screw rod plastic extruder squeezes out, and the mixture is from charging
The extrusion temperature of mouth to head is followed successively by 120 DEG C~140 DEG C~140 DEG C, obtains bar, is suppressed with 120 DEG C of vulcanizing press
Film forming, obtains thermoplastic starch film.
Comparative example 7
A kind of composite membrane of polyvinyl alcohol is prepared by the following method to obtain:
It dissolves polyvinyl alcohol in 80 DEG C of hot water, polyvinyl alcohol weight 5%, 30% weight of polyvinyl alcohol is added
Unmodified hollow glass microbead is added in above-mentioned solution by glycerol, and the weight of unmodified hollow glass microbead is polyvinyl alcohol
The 10% of weight continues to stop heating, pour into mold, dry 4 is small at 60 DEG C after stirring is uniformly dispersed to hollow glass microbead
When, obtain composite membrane of polyvinyl alcohol.
Comparative example 8
A kind of composite membrane of polyvinyl alcohol, preparation method is identical as comparative example 7, the difference is that, will not it change in comparative example 7
The 20% of the Change Weight To polyvinyl alcohol weight of property hollow glass microbead, other conditions are constant.
Comparative example 9
A kind of composite membrane of polyvinyl alcohol, preparation method is identical as comparative example 7, the difference is that, will not it change in comparative example 7
Property hollow glass microbead be changed to the modified hollow glass microbead of sodium hydroxide obtained in comparative example 1, other conditions are constant.
Comparative example 10
A kind of composite membrane of polyvinyl alcohol, preparation method is identical as comparative example 9, the difference is that, by hydrogen-oxygen in comparative example 9
Change the 20% of the Change Weight To polyvinyl alcohol weight of the modified hollow glass microbead of sodium, other conditions are constant.
Comparative example 11
A kind of polyvinyl alcohol film, is prepared only with polyvinyl alcohol.Specifically includes the following steps: polyvinyl alcohol is dissolved
In 80 DEG C of hot water, the glycerol of 30% weight of polyvinyl alcohol is added in polyvinyl alcohol weight 5%, is continued stirring 1 hour, is stopped
It only heats, pours into mold, it is 4 hours dry at 60 DEG C, obtain polyvinyl alcohol film.
Comparative test: the starch composite membrane chosen in embodiment 6-10 and comparative example 2-6 respectively does performance test, then distinguishes
The composite membrane of polyvinyl alcohol chosen in embodiment 11-14 and comparative example 7-11 does performance test, is as a result listed in table 1-4.
Test explanation:
1. Mechanics Performance Testing
Starch composite membrane sample in all embodiments saves 48h in the environment of relative humidity (RH) 50%, after taking-up
Measurement.The thickness of starch composite membrane takes 5 points to measure at random on each sample to be tested, is finally averaged.According to
GB1040-79 carries out tensile property test；Sample is measured with electronic tension tester, rate of extension is 50 millis when test
M/min.Each sample average measures 6 times, is averaged.
2. water vapour permeability is tested
By anhydrous CaC12Dry 2h, then weighs the anhydrous CaC of 5g in 105 DEG C of baking ovens12It is placed in weighing bottle, and will be to
Sample is closely covered on weighing bottleneck, is sealed with all-purpose adhesive, by weighing bottle be put into relative humidity (RH) be 75% it is closed
In container, to keep sample two sides psychrometric difference for 75%.Increased by the quality of weighing bottle and measures water vapour transit dose.For 24 hours
Within weigh 8 times, weighing be accurate to 0.0001g.
Mass change is plotted against time, and is straight line (r2> 0.99), water vapour permeability (WVTR) thus straight line is oblique
Rate (g/s) is by effective transmission area (m2) remove and calculate.
Its calculation formula is as follows:
Wherein, WVP is water vapour permeability, unit g s-1m-1Pa-1；S is the saturated vapor pressure for measuring temperature and being lauched, single
Position Pa；R1For ambient humidity；R2For humidity in weighing bottle；S (R1-R2) is 1753.55 under this paper measuring condition；D is film thickness,
Unit m.Each sample average is done 5 times, is averaged.
1 starch composite membrane mechanical property of table
2 starch composite membrane water vapour permeability of table
3 composite membrane of polyvinyl alcohol mechanical property of table
4 composite membrane of polyvinyl alcohol water vapour permeability of table
1. the performance of starch composite membrane
A tensile strength: (1) when in starch composite membrane contain identical additive amount and the identical modified hollow glass of type it is micro-
When pearl, the tensile strength that starch composite membrane wants humidity ratio when humidity is 50% when being 75% is big；It (2) is 50% in humidity
Under the conditions of, the tensile strength for adding the starch composite membrane of modified hollow glass microbead and unmodified hollow glass microbead is all larger than
Pure thermoplastic starch film；(3) when humidity is 50% and modified hollow glass microbead additive amount is 10%, starch composite membrane
Tensile strength order are as follows: the modified hollow glass microbead of starch conversion hollow glass microbead > monoxone > sodium hydroxide modification is hollow
Glass microballoon > unmodified hollow glass microbead；(4) under conditions of humidity is 75%, the modified hollow glass of addition sodium hydroxide
Microballon or starch conversion hollow glass microbead cause the tensile strength of starch composite membrane to be greater than the thermoplastic starch in comparative example 6
Film, the addition of unmodified hollow glass microbead cause the tensile strength of starch composite membrane to be less than the thermoplastic starch in comparative example 6
Powder film；(5) under same damp condition, the tensile strength of the starch composite membrane of starch conversion hollow glass microbead is added most
Greatly, and the tensile strength of the starch composite membrane of 10% additive amount is maximum.
B elongation at break: (1) elongation at break of the starch composite membrane of hollow glass microbead is added than in comparative example 6
Thermoplastic starch composite membrane elongation at break it is small；(2) under conditions of humidity is 50%, in adding same amount of modification
In the case of empty glass microballoon, the elongation at break order of starch composite membrane: unmodified hollow glass microbead < sodium hydroxide is modified
Hollow glass microbead < monoxone is modified hollow glass microbead < starch conversion hollow glass microbead；(3) under same humidity, add
When adding same modified hollow glass microbead, the elongation at break of starch composite membrane is greater than 20% in 10% additive amount.
C water vapour permeability: (1) after unmodified hollow glass microbead addition, on the water vapour permeability of starch composite membrane
It rises；(2) the modified hollow glass microbead of addition sodium hydroxide, the modified hollow glass microbead of monoxone and starch conversion hollow glass are micro-
The water vapour permeability of the starch composite membrane of pearl is less than the transmitance of the thermoplastic starch film in comparative example 6；(3) 10% additive amounts
Starch conversion hollow glass microbead starch composite membrane water vapour permeability it is minimum.
2. the performance of composite membrane of polyvinyl alcohol
A tensile strength: (1) when in composite membrane of polyvinyl alcohol contain identical additive amount and the hollow glass of the identical modification of type
When glass microballon, the tensile strength that composite membrane of polyvinyl alcohol wants humidity ratio when humidity is 50% when being 75% is big；(2) addition is same
Under conditions of the modification hollow glass microbead of sample, the tensile strength of the composite membrane of polyvinyl alcohol of 10% additive amount is greater than 20% and adds
The composite membrane of polyvinyl alcohol of dosage；(3) under conditions of adding same amount of various modified hollow glass microbeads, polyvinyl alcohol is multiple
Close the tensile strength order of film are as follows: the modified hollow glass microbead > hydroxide of polyvinyl alcohol modification hollow glass microbead > monoxone
Sodium is modified hollow glass microbead > unmodified hollow glass microbead；(4) under same damp condition, 10% polyvinyl alcohol is added
The tensile strength of the composite membrane of polyvinyl alcohol of modified hollow glass microbead is maximum.
B elongation at break: (1) adding modified hollow glass microbead and the polyvinyl alcohol of unmodified hollow glass microbead is compound
The elongation at break of film is respectively less than the elongation at break of the polyvinyl alcohol film in comparative example 11；(2) condition for being 50% in humidity
Under, when adding same amount of various modified hollow glass microbeads, the elongation at break order of composite membrane of polyvinyl alcohol: hydroxide
The modified unmodified hollow glass microbead < polyvinyl alcohol modification of hollow glass microbead < of the modified hollow glass microbead < monoxone of sodium
Hollow glass microbead；(3) under same humidity, when adding same modified hollow glass microbead, composite membrane of polyvinyl alcohol breaks
It splits elongation and is greater than 20% in 10% additive amount.
C water vapour permeability: (1) composite membrane of polyvinyl alcohol for the various modified hollow glass microbeads that additive amount is 10%
Water vapour permeability is below the polyvinyl alcohol film in comparative example 6；(2) the poly- second of polyvinyl alcohol modification hollow glass microbead is added
The water vapour permeability of enol composite membrane is declined；(3) in the case where same humidity and identical additive amount, polyvinyl alcohol
The water vapour permeability order of composite membrane: the modified hollow glass microbead < hydrogen of polyvinyl alcohol modification hollow glass microbead < monoxone
Sodium oxide molybdena is modified the unmodified hollow glass microbead of hollow glass microbead <.
Conclusion and analysis
For synthesis, starch composite membrane and the tensile strength of composite membrane of polyvinyl alcohol are wanted under conditions of humidity is 50%
Bigger than tensile strength under conditions of humidity is 75%, elongation at break is then opposite；It may be since humidity is excessive, in water
There is also hydroxyls, keep hollow glass microbead and the hydroxy combining in water excessive, affect hollow glass microbead and starch or poly-
The combination of vinyl alcohol, to affect the tensile strength and elongation at break of starch composite membrane or composite membrane of polyvinyl alcohol.
The addition of modified hollow glass microbead increases starch composite membrane and the tensile strength of composite membrane of polyvinyl alcohol, this
It is to increase interaction since there are great amount of hydroxy group in hydroxyl, with degradative membrane to form hydrogen bond on modified hollow glass microbead surface,
Modified hollow glass microbead plays the role of skeleton in degradative membrane and increases intensity.
For starch composite membrane, under different humidity, the starch composite membrane of 10% starch conversion hollow glass microbead is added
Tensile strength is maximum, and moisture-vapor transmission is minimum, best performance；For composite membrane of polyvinyl alcohol, under different humidity, addition
The tensile strength of the composite membrane of polyvinyl alcohol of 10% polyvinyl alcohol modification hollow glass microbead is maximum, and moisture-vapor transmission is most
It is small, best performance；Modified hollow glass microbead plays skeleton in starch composite membrane or composite membrane of polyvinyl alcohol and increases intensity
Effect, simultaneously because starch conversion hollow glass microbead or polyvinyl alcohol modification hollow glass microbead are in hydrophily degradation film base material
There is preferable dispersibility in material, when making water vapour through starch composite membrane or composite membrane of polyvinyl alcohol, starch conversion hollow glass
Microballon or polyvinyl alcohol modification hollow glass microbead play inhibition, therefore moisture-vapor transmission reduces.
It is hollow for the starch composite membrane or polyvinyl alcohol modification of adding the starch conversion hollow glass microbead of 20% content
In the composite membrane of polyvinyl alcohol of glass microballoon, since additive amount is more, modified hollow glass microbead is likely to occur agglomeration, makes
Membrane material generates local defect, so as to cause the decline of composite membrane part tensile strength, compound film-strength as a result occurs and increases sometimes
Add unconspicuous phenomenon.Similarly, since excessive modification hollow glass microbead is reunited, to the drag effect of water vapour transmission
It has an impact, so that water vapour permeability be made irregular phenomenon occur.On the other hand, modified hollow glass microbead additive amount mistake
More, the content of starch or polyvinyl alcohol is opposite in membrane material is reduced, to reduce the performance of resin itself in membrane material.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that without departing substantially from of the invention
Many other change and modification can be made in the case where spirit and scope.It is, therefore, intended that in the following claims
Including belonging to all such changes and modifications in the scope of the invention.
Claims (33)
1. a kind of method of modifying of hollow glass microbead, which is characterized in that including by the surface of hollow glass microbead and monoxone
Solution contact, obtains the step of monoxone is modified hollow glass microbead, optionally, further includes:
The solid mixture obtained after the modified hollow glass microbead of monoxone is mixed with starch be placed in including water, ammonia spirit and
It is reacted in the mixed solution of hydrazine hydrate solution, obtains starch conversion hollow glass microbead；
Or,
The solid mixture obtained after the modified hollow glass microbead of monoxone and polyvinyl alcohol is placed in molten including water, ammonium hydroxide
It is reacted in liquid and the mixed solution of hydrazine hydrate solution, obtains polyvinyl alcohol modification hollow glass microbead.
2. the method for modifying of hollow glass microbead according to claim 1, which is characterized in that described by hollow glass microbead
Surface contact with chloroacetic acid solution the following steps are included: hollow glass microbead is placed in chloroacetic acid solution and react, so
Hollow glass microbead is modified by monoxone is obtained after washing and drying.
3. the method for modifying of hollow glass microbead according to claim 2, which is characterized in that the matter of the chloroacetic acid solution
Amount score is 0.1-5%.
4. the method for modifying of hollow glass microbead according to claim 2, which is characterized in that the hollow glass microbead is set
Reaction condition when being reacted in chloroacetic acid solution are as follows: react 0.5-2h under the conditions of 0-60 DEG C.
5. the method for modifying of hollow glass microbead according to claim 2, which is characterized in that the hollow glass microbead with
It further include thering is the mixture to hollow glass microbead and chloroacetic acid solution to filter before washing after the chloroacetic acid solution reaction
Operation.
6. the method for modifying of hollow glass microbead according to claim 5, which is characterized in that the drying is dry for vacuum
It is dry.
7. the method for modifying of hollow glass microbead according to claim 1, which is characterized in that with aqueous slkali to hollow glass
Microballon again contacts on the surface of hollow glass microbead with chloroacetic acid solution after being cleaned.
8. the method for modifying of hollow glass microbead according to claim 7, which is characterized in that with aqueous slkali to hollow glass
Microballon is cleaned, comprising the following steps: is mixed hollow glass microbead with aqueous slkali, ultrasonic mixing handles 0.1-2h, then
It flows back under the conditions of 50-90 DEG C of oil bath, mechanical stirring 0.1-2h.
9. the method for modifying of hollow glass microbead according to claim 8, which is characterized in that the quality of the aqueous slkali point
Number is 0.5-5%.
10. the method for modifying of hollow glass microbead according to claim 9, which is characterized in that the aqueous slkali includes hydrogen
One of sodium hydroxide solution, potassium hydroxide solution, sodium carbonate liquor or solution of potassium carbonate or at least two combination.
11. the method for modifying of -10 described in any item hollow glass microbeads according to claim 1, which is characterized in that water, ammonium hydroxide
The volume ratio of solution and hydrazine hydrate solution is 100:(5-20): 1.
12. the method for modifying of hollow glass microbead according to claim 11, which is characterized in that water, ammonia spirit and water
The volume ratio for closing hydrazine solution is 100:(5-15): 1.
13. the method for modifying of hollow glass microbead according to claim 12, which is characterized in that water, ammonia spirit and water
The volume ratio for closing hydrazine solution is 100:10:1.
14. the method for modifying of hollow glass microbead according to claim 11, which is characterized in that the matter of the ammonia spirit
Amount score is 20%-30%.
15. the method for modifying of hollow glass microbead according to claim 11, which is characterized in that the hydrazine hydrate solution
Mass fraction is 75-85%.
16. the method for modifying of -10 described in any item hollow glass microbeads according to claim 1, which is characterized in that the mixing
The mass ratio of solution and the solid mixture is (5-20): 1.
17. the method for modifying of hollow glass microbead according to claim 16, which is characterized in that the mixed solution and institute
The mass ratio for stating solid mixture is (5-15): 1.
18. the method for modifying of hollow glass microbead according to claim 17, which is characterized in that the mixed solution and institute
The mass ratio for stating solid mixture is 10:1.
19. the method for modifying of -10 described in any item hollow glass microbeads according to claim 1, which is characterized in that the solid
The step of mixture is reacted in the mixed solution includes: that the solid mixture is placed in after the mixed solution and first stirs
20-40min is mixed, then reacts 3-5h at 70-100 DEG C.
20. a kind of modified hollow glass microbead, which is characterized in that including according to claim 1-19 described in any item hollow glass
The modified hollow glass microbead of monoxone or starch conversion hollow glass microbead or polyethylene is prepared in the method for modifying of glass microballon
Alcohol is modified hollow glass microbead.
21. a kind of preparation method of starch composite membrane, which comprises the following steps: by glycerol, starch and claim
The modified hollow glass microbead of monoxone described in 20 or the mixing of starch conversion hollow glass microbead, obtain after extrusion and compacting
The starch composite membrane.
22. the preparation method of starch composite membrane according to claim 21, which comprises the following steps: first will
Glycerol and starch mixing add the modified hollow glass microbead of monoxone or starch conversion hollow glass microbead, are squeezed out and pressed
The starch composite membrane is obtained after system.
23. the preparation method of starch composite membrane according to claim 22, which is characterized in that mixing machine used when mixing
Revolving speed is 2500-4000r/min.
24. the preparation method of starch composite membrane according to claim 22, which is characterized in that the glycerol and the starch
Mass ratio be (0.1-0.5): 1.
25. the preparation method of starch composite membrane according to claim 24, which is characterized in that the glycerol and the starch
Mass ratio be (0.2-0.4): 1.
26. the preparation method of starch composite membrane according to claim 25, which is characterized in that the glycerol and the starch
Mass ratio be 0.3:1.
27. the preparation method of starch composite membrane according to claim 22, which is characterized in that during the monoxone of addition is modified
The quality of empty glass microballoon or starch conversion hollow glass microbead accounts for the 1-20% of the starch quality.
28. a kind of preparation method of composite membrane of polyvinyl alcohol, which comprises the following steps: by polyvinyl alcohol, glycerol and
The modified hollow glass microbead of monoxone described in claim 20 or polyvinyl alcohol modification hollow glass microbead are dissolved in hot water,
Through being dried to obtain composite membrane of polyvinyl alcohol after stirring evenly.
29. the preparation method of composite membrane of polyvinyl alcohol according to claim 28, which comprises the following steps:
First polyvinyl alcohol is added in hot water, glycerol is successively added into solution again after polyvinyl alcohol dissolution completely and monoxone is modified
Hollow glass microbead or polyvinyl alcohol modification hollow glass microbead, stirring to the modified hollow glass microbead of monoxone or polyvinyl alcohol
Modified hollow glass microbead stops heating after being uniformly dispersed, and acquired solution is poured into mold and is dried, after demoulding
To the composite membrane of polyvinyl alcohol.
30. the preparation method of composite membrane of polyvinyl alcohol according to claim 29, which is characterized in that heat is added in polyvinyl alcohol
The mass concentration of polyvinyl alcohol is 1-10% in the solution obtained after in water.
31. the preparation method of composite membrane of polyvinyl alcohol according to claim 29, which is characterized in that the glycerol is poly- second
The 1-30% of enol weight.
32. the preparation method of composite membrane of polyvinyl alcohol according to claim 29, which is characterized in that the monoxone is modified
Hollow glass microbead or polyvinyl alcohol modification hollow glass microbead are the 1-20% of polyvinyl alcohol weight.
33. the preparation method of composite membrane of polyvinyl alcohol according to claim 29, which is characterized in that drying temperature when dry
It is 50-80 DEG C, drying time 2-5h.
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