CN104119541B - A kind of preparation method of modified PVA membrane solution - Google Patents
A kind of preparation method of modified PVA membrane solution Download PDFInfo
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- CN104119541B CN104119541B CN201410303000.9A CN201410303000A CN104119541B CN 104119541 B CN104119541 B CN 104119541B CN 201410303000 A CN201410303000 A CN 201410303000A CN 104119541 B CN104119541 B CN 104119541B
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Abstract
The invention discloses the preparation method of a kind of modified PVA membrane solution, relate to field of papermaking, described method includes: provide hyper-branched polyester；In polyvinyl alcohol water solution, add described hyper-branched polyester and polar organic solvent, react under predetermined circumstances, it is thus achieved that the first mixture；Filter described first mixture, it is thus achieved that the first solution；In described first solution, add crosslinking agent, it is thus achieved that the second solution, stir described second solution to mixing and obtain described modified PVA membrane solution.By said method, the present invention can improve penetrating amount and the mechanicalness of polyvinyl alcohol film, and nonhazardous.
Description
Technical field
The present invention relates to pulp technology for making paper, particularly relate to a kind of modified PVA membrane solution
Preparation method.
Background technology
Polyvinyl alcohol (PVA) low price, stable chemical nature, have height hydrophily,
Good film forming and stain resistance, be therefore widely used as sheet processing raw material.But polyethylene
Alcohol film forming porosity is low, and penetrating amount is less, and polyvinyl alcohol film is the most swelling in water, and mechanicalness is relatively
Difference, it is therefore desirable to be modified overcoming drawbacks described above to PVA.
In prior art, PVA modification is mainly used the PVA ethylidene ether modification skill based on formaldehyde
Art.But in PVA ethylidene ether modification, residual formaldehyde amount can not eliminate so that modified product is using
During easy release formaldehyde, and formaldehyde have acute toxicity, mutagenicity, genotoxicity and
Carcinogenicity etc. endanger, unfavorable to health.
Summary of the invention
The technical problem that present invention mainly solves is to provide the system of a kind of modified PVA membrane solution
Preparation Method, it is possible to increase the penetrating amount of polyvinyl alcohol film and mechanicalness, and nonhazardous.
For solving above-mentioned technical problem, the technical scheme that the present invention uses is: provide one to change
The preparation method of property polyvinyl alcohol coating solution, described method includes:
Hyper-branched polyester is provided；
Described hyper-branched polyester and polar organic solvent is added, predetermined in polyvinyl alcohol water solution
Under conditions of react, it is thus achieved that the first mixture, described polar organic solvent is miscible with water, for molten
Solve described hyper-branched polyester；
Filter described first mixture, it is thus achieved that the first solution；
In described first solution, add crosslinking agent, it is thus achieved that the second solution, stir described second solution
Described modified PVA membrane solution is obtained to mixing.
Wherein, described polar organic solvent is dimethyl sulfoxide (DMSO).
Wherein, described predetermined condition includes: be placed in the stirred in water bath 2 hours of 70-80 degree Celsius,
It is then cooled to room temperature.
Wherein, the amount of described hyper-branched polyester is 40-60 mass parts, the amount of described dimethyl sulfoxide (DMSO)
It is 80 mass parts.
Wherein, described in described polyvinyl alcohol water solution, described hyper-branched polyester is added and polarity has
Before the step of machine solvent, including:
The polyvinyl alcohol of 100 mass parts is joined in the water of 500 mass parts, at 60 degrees Celsius
At a temperature of be incubated 30 minutes, be configured to polyvinyl alcohol water solution.
Wherein, the step of described offer hyper-branched polyester includes:
Pentaerythrite, 2-tartronic acid and p-methyl benzenesulfonic acid are added in reaction vessel；
In described reaction vessel, it is passed through nitrogen, and described reaction vessel is warming up to 110～125
Degree Celsius, reaction 1.5 hours at ambient pressure；
Stopping being passed through nitrogen to described reaction vessel, described reaction is also held by airtight described reaction vessel
Pressure in device is reduced to 1 kPa, continues reaction 2 hours, obtains described hyper-branched polyester.
Wherein, the amount of described pentaerythrite is 5～10 mass parts, the amount of described 2-tartronic acid
Being 100 mass parts, the amount of described p-methyl benzenesulfonic acid is 0.5 mass parts.
Wherein, the alcoholysis degree of described polyvinyl alcohol is 74%.
Wherein, described crosslinking agent is acrylic acid.
Wherein, described acrylic acid amount is 2 mass parts.
The invention has the beneficial effects as follows: be different from the situation of prior art, the present invention uses hyperbranched
Polyester modified polyethylene alcohol, hyper-branched polyester has three dimensions stereochemical structure and highly branched,
Adding a certain amount of hyper-branched polyester and crosslinking agent in polyvinyl alcohol water solution, polyvinyl alcohol is with hyperbranched
Polyester blend also cross-links, and is strutted with high functionality by the three dimensions stereochemical structure of hyper-branched polyester
Compact texture during polyvinyl alcohol film forming, thus improve permeability and the mechanicalness of polyvinyl alcohol film
Can, avoid the murder by poisoning that modified formaldehyde brings to health simultaneously.
Accompanying drawing explanation
Fig. 1 is the stream of preparation method one embodiment of the present invention a kind of modified PVA membrane solution
Cheng Tu；
Fig. 2 is another embodiment of preparation method of the present invention a kind of modified PVA membrane solution
Flow chart.
Detailed description of the invention
The present invention is described in detail with embodiment below in conjunction with the accompanying drawings.
Real refering to the preparation method one that Fig. 1, Fig. 1 are the present invention a kind of modified PVA membrane solution
Execute the flow chart of mode, the preparation method bag of embodiment of the present invention modified PVA membrane solution
Include:
Step S101: hyper-branched polyester is provided；
Hyper-branched polyester is to have three-dimensional structure, highly branched synthesis macromolecule, and line style to gather
Compound is different, and it has high functionality, viscosity is low, intersolubility good, active high characteristic.
Step S102: add hyper-branched polyester and polar organic solvent in polyvinyl alcohol water solution,
Reacting under predetermined circumstances, it is thus achieved that the first mixture, polar organic solvent is miscible with water, is used for
Dissolve hyper-branched polyester；
Be dissolved in polar organic solvent owing to hyper-branched polyester is substantially insoluble in water, polyvinyl alcohol is basic
Miscible with water insoluble in organic solvent, thus embodiment of the present invention hyper-branched polyester is dissolved in
The polar organic solvent that water dissolves each other, is then added in polyvinyl alcohol water solution, makes hyper-branched polyester
It is fully contacted with polyvinyl alcohol.
Wherein, polar organic solvent is dimethyl sulfoxide (DMSO), in other embodiment of the present invention, also
Other can be used to dissolve hyper-branched polyester and organic solvent miscible with water, such as acetone, diformazan
Base formamide, dimethylacetylamide and hexamethyl phosphoramide etc..
Wherein, predetermined condition includes: the stirred in water bath 2 being placed in 70-80 degree Celsius (DEG C) is little
Time (h), be then cooled to room temperature, bath temperature can be 70 degrees Celsius, 75 degrees Celsius, 80
Degree Celsius etc., stirring two hours is to make hyper-branched polyester in polar organic solvent in a water bath
Fully dissolve, and be fully contacted with polyvinyl alcohol；In general, room temperature has determining of 3 kinds of scopes
Justice: 23 DEG C ± 2 DEG C；25℃±5℃；20℃±5℃.
Wherein, the amount of hyper-branched polyester is 40-60 mass parts, such as, and 40 mass parts, 50 mass
Part, 60 mass parts etc., the amount of dimethyl sulfoxide (DMSO) is 80 mass parts.
Wherein, in polyvinyl alcohol water solution, hyper-branched polyester and the step of polar organic solvent are being added
Before Zhou, the polyvinyl alcohol of 100 mass parts joined in the water of 500 mass parts, take the photograph 60
It is incubated 30 minutes at a temperature of family name's degree, is configured to polyvinyl alcohol water solution；Wherein polyvinyl alcohol
Alcoholysis degree is 74%；Embodiment of the present invention uses alcoholysis degree to be the polyvinyl alcohol of 74%, its reaction
Effect is preferable, and is configured to the polyvinyl alcohol water solution of higher concentration, to be finally made
The ink jet printing performance of paper is helpful, and printing effect is than using other alcoholysis degrees and the poly-second of concentration
The paper that the enol aqueous solution is made is clear, and color saturation is high.
Step S103: filter the first mixture, it is thus achieved that the first solution；
Filtering the first mixture is to filter out hyper-branched polyester and polyethylene in the first mixture
Water insoluble or the insoluble matter of polar organic solvent and unreacted produced by alcohol generation side reaction
Complete hyper-branched polyester, filter method conventional in wherein filtration step uses this area.
Step S104: adding crosslinking agent in the first solution, it is thus achieved that the second solution, stirring second is molten
Liquid obtains modified PVA membrane solution to mixing.
The reactivity directly reacted due to polyvinyl alcohol and hyper-branched polyester is the lowest, is cross-linked by addition
Agent, makes hyper-branched polyester fully be combined with polyvinyl alcohol.
Wherein, crosslinking agent is acrylic acid；In other embodiment of the present invention, crosslinking agent can also
For other acrylic crosslinking agent, such as hydroxy-ethyl acrylate, methacrylic acid, methacrylic acid
Hydroxyl ethyl ester and N hydroxymethyl acrylamide etc..The crosslinking agent acrylic acid reaction of embodiment of the present invention
Activity is high, and its side reaction nonhazardous.
Wherein, acrylic acid amount is 2 mass parts.
Being different from prior art, embodiment of the present invention uses hyper-branched polyester modified polyvinylalcohol,
Hyper-branched polyester has three dimensions stereochemical structure and highly branched, adds in polyvinyl alcohol water solution
Entering a certain amount of hyper-branched polyester and crosslinking agent, polyvinyl alcohol is blended with hyper-branched polyester and cross-links, logical
Cross when the three dimensions stereochemical structure of hyper-branched polyester and high functionality strut polyvinyl alcohol film forming
Compact texture, thus improve permeability and the mechanical performance of polyvinyl alcohol film, avoid formaldehyde simultaneously
The modified murder by poisoning brought to health.
Refering to the preparation method that Fig. 2, Fig. 2 are the present invention a kind of modified PVA membrane solution another
The flow chart of embodiment, the preparation method bag of embodiment of the present invention modified PVA membrane solution
Include:
Step S201: pentaerythrite, 2-tartronic acid and p-methyl benzenesulfonic acid are added reaction vessel
In；
Step S202: be passed through nitrogen in reaction vessel, and reaction vessel is warming up to 110～125
Degree Celsius, reaction 1.5 hours at ambient pressure；
Nitrogen is inert gas, is passed through nitrogen for the air driving away in container, it is to avoid in air
The reaction carried out in oxygen interference reaction vessel, in other embodiment of the present invention, it is possible to instead
Answer and container is passed through other inert gases, such as: argon gas etc.；Reaction vessel can be warming up to 110
Degree Celsius, 120 degrees Celsius, 125 degrees Celsius etc.；Normal pressure refers to an atmospheric pressure, and i.e. we put down
The gas pressure that often this atmosphere of life produces；In embodiment of the present invention, whole hyperbranched
Course of reaction completes in the environment of nitrogen charging, and polymerizing condition is harsh, is substantially shorter the reaction time,
And it is easy and simple to handle.
Step S203: stop being passed through nitrogen to reaction vessel, closed reaction vessel by reaction vessel
Interior pressure is reduced to 1 kPa, continues reaction 2 hours, obtains hyper-branched polyester；
In reaction vessel, it is a centronucleus with pentaerythrite, under the catalysis of p-methyl benzenesulfonic acid,
The 2-tartronic acid added extends from inside to outside around four alcoholic extract hydroxyl groups of pentaerythrite, finally leads to
Too much generation condensation forms highly branched hyper-branched polyester, and this hyper-branched polyester is to have three-dimensional structure
, highly branched synthesis macromolecule, different from linear polymer, it has high functionality, glutinous
Spend low, intersolubility good, active high characteristic, 2-tartronic acid is side chain steam, and it is with it
Distinctive binary acid structure is brought bigger sterically hindered, constitutes the loosest three dimensions three-dimensional
Structure so that the hyper-branched polyester that final condensation is formed have highly-branched degree, more preferable dissolubility,
The features such as lower viscosity, and generated time is greatly shortened.
Wherein, the amount of pentaerythrite is 5～10 mass parts, and the amount of 2-tartronic acid is 100 matter
Amount part, the amount of p-methyl benzenesulfonic acid is 0.5 mass parts；The amount of pentaerythrite can be 5 mass parts, 7
Mass parts, 10 mass parts etc..
Step S204: add hyper-branched polyester and polar organic solvent in polyvinyl alcohol water solution,
Reacting under predetermined circumstances, it is thus achieved that the first mixture, polar organic solvent is miscible with water, is used for
Dissolve hyper-branched polyester；
Wherein, polar organic solvent is dimethyl sulfoxide (DMSO), in other embodiment of the present invention, also
Other can be used to dissolve hyper-branched polyester and solvent miscible with water, such as acetone, acetonitrile, two
NMF, dimethylacetylamide and hexamethyl phosphoramide etc..
Wherein, predetermined condition includes: be placed in the stirred in water bath 2 hours of 70-80 degree Celsius, so
After be cooled to room temperature, bath temperature can be 70 degrees Celsius, 75 degrees Celsius or 80 degrees Celsius etc.,
Stirring two hours is to make hyper-branched polyester fully dissolve in polar organic solvent in a water bath,
And being fully contacted with polyvinyl alcohol, room temperature is 25 degrees Celsius.
Wherein, the amount of hyper-branched polyester is 40-60 mass parts, and the amount of dimethyl sulfoxide (DMSO) is 80 mass
Part；Wherein the amount of hyper-branched polyester can be 40 mass parts, 50 mass parts or 60 mass parts etc..
Wherein, in polyvinyl alcohol water solution, hyper-branched polyester and the step of polar organic solvent are being added
Before Zhou, the polyvinyl alcohol of 100 mass parts joined in the water of 500 mass parts, take the photograph 60
It is incubated 30 minutes at a temperature of family name's degree, is configured to polyvinyl alcohol water solution；Wherein polyvinyl alcohol
Alcoholysis degree is 74%.
Step S205: filter the first mixture, it is thus achieved that the first solution；
Filtering the first mixture is to filter out hyper-branched polyester and polyethylene in the first mixture
Water insoluble or the insoluble matter of polar organic solvent and unreacted produced by alcohol generation side reaction
Complete hyper-branched polyester, filter method conventional in wherein filtration step uses this area.
Step S206: adding crosslinking agent in the first solution, it is thus achieved that the second solution, stirring second is molten
Liquid obtains modified PVA membrane solution to mixing.
The reactivity directly reacted due to polyvinyl alcohol and hyper-branched polyester is the lowest, is cross-linked by addition
Agent, makes hyper-branched polyester fully be combined with polyvinyl alcohol.
Wherein, crosslinking agent is acrylic acid；In other embodiments of the present invention, crosslinking agent can also
For other acrylic crosslinking agent, such as hydroxy-ethyl acrylate, methacrylic acid, methacrylic acid
Hydroxyl ethyl ester and N hydroxymethyl acrylamide etc..
Wherein, acrylic acid amount is 2 mass parts.
Being different from prior art, embodiment of the present invention uses hyper-branched polyester modified polyvinylalcohol,
Hyper-branched polyester has three dimensions stereochemical structure and highly branched, adds in polyvinyl alcohol water solution
Entering a certain amount of hyper-branched polyester and crosslinking agent, polyvinyl alcohol is blended with hyper-branched polyester and cross-links, logical
Cross the loose three dimensions stereochemical structure of hyper-branched polyester to strut polyvinyl alcohol with high functionality and become
Compact texture during film, thus improve permeability and the mechanical performance of polyvinyl alcohol film, hyperbranched poly
The carboxylic acid group of ester peripheral ends also has high activity and easy modification, can promote the affinity of film, with
Time present invention, avoiding the murder by poisoning that modified formaldehyde brings to health.
Below by the detailed description of the invention preparation method to modified PVA membrane solution of the present invention
It is described further.
Embodiment 1
By 5 mass parts pentaerythrites, 100 mass parts 2-tartronic acids and 0.5 mass parts to first
Benzene sulfonic acid adds in reaction vessel, is passed through nitrogen, and is warming up to by reaction vessel in reaction vessel
110 degrees Celsius, reaction 1.5 hours at ambient pressure, stop being passed through nitrogen to reaction vessel, airtight
Pressure in reaction vessel is also reduced to 1 kPa by reaction vessel, continues reaction 2 hours, obtains
Hyper-branched polyester；
The polyvinyl alcohol that the degree of polymerization is 700 of 100 mass parts is joined in the water of 500 mass parts,
Insulation 30 minutes, are configured to polyvinyl alcohol water solution at a temperature of 60 degrees c；
The hyper-branched polyester and the two of 80 mass parts of 40 mass parts is added in polyvinyl alcohol water solution
Methyl sulfoxide, is placed in the stirred in water bath 2 hours of 70 degrees Celsius, is then cooled to room temperature, obtains
Obtain the first mixture, filter the first mixture, it is thus achieved that the first solution, in the first solution, add 2
The acrylic acid of mass parts, it is thus achieved that the second solution, stir the second solution to mix obtain modified poly-
Vinyl alcohol coating solution.
Embodiment 2
By 8 mass parts pentaerythrites, 100 mass parts 2-tartronic acids and 0.5 mass parts to first
Benzene sulfonic acid adds in reaction vessel, is passed through nitrogen, and is warming up to by reaction vessel in reaction vessel
120 degrees Celsius, reaction 1.5 hours at ambient pressure, stop being passed through nitrogen to reaction vessel, airtight
Pressure in reaction vessel is also reduced to 1 kPa by reaction vessel, continues reaction 2 hours, obtains
Hyper-branched polyester；
The polyvinyl alcohol that the degree of polymerization is 700 of 100 mass parts is joined in the water of 500 mass parts,
Insulation 30 minutes, are configured to polyvinyl alcohol water solution at a temperature of 60 degrees c；
The hyper-branched polyester and the two of 80 mass parts of 45 mass parts is added in polyvinyl alcohol water solution
Methyl sulfoxide, is placed in the stirred in water bath 2 hours of 75 degrees Celsius, is then cooled to room temperature, obtains
Obtain the first mixture, filter the first mixture, it is thus achieved that the first solution, in the first solution, add 2
The acrylic acid of mass parts, it is thus achieved that the second solution, stir the second solution to mix obtain modified poly-
Vinyl alcohol coating solution.
Embodiment 3
By 8 mass parts pentaerythrites, 100 mass parts 2-tartronic acids and 0.5 mass parts to first
Benzene sulfonic acid adds in reaction vessel, is passed through nitrogen, and is warming up to by reaction vessel in reaction vessel
120 degrees Celsius, reaction 1.5 hours at ambient pressure, stop being passed through nitrogen to reaction vessel, airtight
Pressure in reaction vessel is also reduced to 1 kPa by reaction vessel, continues reaction 2 hours, obtains
Hyper-branched polyester；
The polyvinyl alcohol that the degree of polymerization is 700 of 100 mass parts is joined in the water of 500 mass parts,
Insulation 30 minutes, are configured to polyvinyl alcohol water solution at a temperature of 60 degrees c；
The hyper-branched polyester and the two of 80 mass parts of 50 mass parts is added in polyvinyl alcohol water solution
Methyl sulfoxide, is placed in the stirred in water bath 2 hours of 75 degrees Celsius, is then cooled to room temperature, obtains
Obtain the first mixture, filter the first mixture, it is thus achieved that the first solution, in the first solution, add 2
The acrylic acid of mass parts, it is thus achieved that the second solution, stir the second solution to mix obtain modified poly-
Vinyl alcohol coating solution.
Embodiment 4
By 10 mass parts pentaerythrites, 100 mass parts 2-tartronic acids and 0.5 mass parts to first
Benzene sulfonic acid adds in reaction vessel, is passed through nitrogen, and is warming up to by reaction vessel in reaction vessel
125 degrees Celsius, reaction 1.5 hours at ambient pressure, stop being passed through nitrogen to reaction vessel, airtight
Pressure in reaction vessel is also reduced to 1 kPa by reaction vessel, continues reaction 2 hours, obtains
Hyper-branched polyester；
The polyvinyl alcohol that the degree of polymerization is 700 of 100 mass parts is joined in the water of 500 mass parts,
Insulation 30 minutes, are configured to polyvinyl alcohol water solution at a temperature of 60 degrees c；
The hyper-branched polyester and the two of 80 mass parts of 60 mass parts is added in polyvinyl alcohol water solution
Methyl sulfoxide, is placed in the stirred in water bath 2 hours of 80 degrees Celsius, is then cooled to room temperature, obtains
Obtain the first mixture, filter the first mixture, it is thus achieved that the first solution, in the first solution, add 2
The acrylic acid of mass parts, it is thus achieved that the second solution, stir the second solution to mix obtain modified poly-
Vinyl alcohol coating solution.
Comparative example 1
By the temperature that the polyvinyl alcohol that the 100 mass parts degree of polymerization are 700 joins 800 mass parts it is
In the running water of 80 degrees Celsius, stirring, it is warming up to 95 degrees Celsius, is incubated 2 hours, treats poly-second
After enol fully dissolves, add 4 mass parts sulfuric acid, 3 mass parts phosphoric acid and 30 mass parts industry first
Aldehyde, controlling pH value is 2 so that it is keep 1.5 hours in 95 degree celsius temperature, carries out condensation anti-
Should, obtain modified PVA membrane solution.
Table 1 is embodiment 1-4 and each raw material addition and reaction condition and film forming in comparative example 1
The performance test results.
Table 1
In table 1, it is big/poor that N represents harmfulness, and+representative harm is less/preferable, ++ represent without danger
Evil/good.
As it can be seen from table 1 pass through the polyvinyl alcohol coating solution that hyperbranched poly is ester modified, to human body
Healthy entirely without harm, and higher mechanical performance and air permeability can be kept.
The foregoing is only embodiments of the present invention, not thereby limit the patent model of the present invention
Enclosing, every equivalent structure utilizing description of the invention and accompanying drawing content to be made or equivalence flow process become
Change, or be directly or indirectly used in other relevant technical fields, be the most in like manner included in the present invention's
In scope of patent protection.
Claims (8)
1. the preparation method of a modified PVA membrane solution, it is characterised in that described method
Including:
Hyper-branched polyester is provided；
Described hyper-branched polyester and polar organic solvent is added, in advance in polyvinyl alcohol water solution
Reacting under conditions of Ding, it is thus achieved that the first mixture, described polar organic solvent is miscible with water, uses
In dissolving described hyper-branched polyester；The alcoholysis degree of described polyvinyl alcohol is 74%；Described predetermined
Condition includes: is placed in the stirred in water bath 2 hours of 70-80 degree Celsius, is then cooled to room temperature；
Filter described first mixture, it is thus achieved that the first solution；
In described first solution, add crosslinking agent, it is thus achieved that the second solution, stir described second molten
Liquid obtains described modified PVA membrane solution to mixing.
Method the most according to claim 1, it is characterised in that described polar organic solvent
It it is dimethyl sulfoxide (DMSO).
Method the most according to claim 2, it is characterised in that described hyper-branched polyester
Amount is 40-60 mass parts, and the amount of described dimethyl sulfoxide (DMSO) is 80 mass parts.
Method the most according to claim 3, it is characterised in that: described to described polyethylene
Before alcohol solution adds the step of described hyper-branched polyester and polar organic solvent, including:
The polyvinyl alcohol of 100 mass parts is joined in the water of 500 mass parts, Celsius 60
It is incubated 30 minutes at a temperature of degree, is configured to polyvinyl alcohol water solution.
Method the most according to claim 1, it is characterised in that described offer hyperbranched poly
The step of ester includes:
Pentaerythrite, 2-tartronic acid and p-methyl benzenesulfonic acid are added in reaction vessel；
In described reaction vessel, it is passed through nitrogen, and described reaction vessel is warming up to 110～125
Degree Celsius, reaction 1.5 hours at ambient pressure；
Stop being passed through nitrogen to described reaction vessel, airtight described reaction vessel by described reaction
Pressure in container is reduced to 1 kPa, continues reaction 2 hours, obtains described hyper-branched polyester.
Method the most according to claim 5, it is characterised in that the amount of described pentaerythrite
Be 5～10 mass parts, the amount of described 2-tartronic acid be 100 mass parts, described to toluene
The amount of sulfonic acid is 0.5 mass parts.
7. according to the method described in claim 1 to 6 any one, it is characterised in that described
Crosslinking agent is acrylic acid.
Method the most according to claim 7, it is characterised in that described acrylic acid amount is
2 mass parts.
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