CN115707734A - Thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability as well as preparation method and application thereof - Google Patents
Thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability, and a preparation method and application thereof. Comprises the following components: the sulfonic acid group copolymerized polyvinyl alcohol is one or a mixture of more of vinyl alcohol-vinyl acetate-sulfonic acid group unsaturated hydrocarbon monomer terpolymers, wherein the polymerization degree of the sulfonic acid group copolymerized polyvinyl alcohol is 500-3500, the content of vinyl alcohol units is 94-99.7 mol%, the total content of vinyl acetate and sulfonic acid group units is 0.3-6 mol%, and the mass fraction of sulfur element is 0.1-4%; the thermoplastic agent is at least one of polyol, polyether polyol or polyol alcoholate; the mass ratio of the sulfonic acid group copolymerized polyvinyl alcohol to the thermoplastic agent is (60-95) to (5-40). The melting point of the prepared thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin is 120-180 ℃, the thermal decomposition temperature is higher than 240 ℃, and the processing window is wide.
Description
Technical Field
The invention relates to the field of processing and preparation of high polymer materials, in particular to a thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability, a preparation method and application thereof.
Background
Polyvinyl alcohol (PVA) has an excellent balance of properties and has gained wide attention and use in recent years. However, due to the structural characteristics of polyhydroxy and strong hydrogen bonds of the molecular chain of PVA, the thermal decomposition temperature is higher than the melting temperature, the thermal plasticizing processing is difficult, and particularly, when the alcoholysis degree is higher, the thermal plasticizing is more difficult, so that the application of PVA is greatly limited. In recent years, a great deal of research work aiming at the thermoplastic processing modification of PVA is carried out at home and abroad, firstly, the melting point is reduced by adding water, polyalcohol, amide and alcohol amine substances and destroying PVA crystals; and secondly, by copolymerization modification, a comonomer with a special group is introduced, so that the hydrogen bond effect in PVA molecules is reduced, and the melting point is further reduced.
The introduction of sulfonic acid group or its salt group which does not react with hydroxyl group into PVA molecular chain can reduce hydrogen bond effect to some extent, but for polyvinyl alcohol with high alcoholysis degree, the problems of narrow thermoplastic processing window and difficult individual thermoplastic processing still exist. Therefore, the development of the polyvinyl alcohol resin with high alcoholysis degree, which can be processed by thermoplasticity, has great application value. Patent CN105440521A discloses a thermoplastic carboxyl-modified polyvinyl alcohol resin with high alcoholysis degree, which realizes thermal plasticizing processing by reducing the melting point of polyvinyl alcohol through carboxyl copolymerization modification group and adding plasticizer, however, on one hand, carboxyl is easy to react with hydroxyl to form lactone to change composition and property, and on the other hand, the formula contains soft water, has low boiling point, and is not beneficial to maintaining the stability in the thermal plasticizing processing process and product use.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability. In particular to a thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability, a preparation method and application thereof, which can realize the anhydrous thermoplastic processing of the copolymerized polyvinyl alcohol with high vinyl alcohol content.
One of the technical problems to be solved by the invention is to provide a thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability, wherein the melting point of the resin is 120-180 ℃, the thermal decomposition temperature is higher than 240 ℃, and the processing window is wide.
The second technical problem to be solved by the invention is to provide a preparation method of thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability corresponding to the first technical problem.
The third technical problem to be solved by the present invention is to provide the thermoplastic sulfonic acid group-copolymerized polyvinyl alcohol resin corresponding to the solution of one of the technical problems or the thermoplastic sulfonic acid group-copolymerized polyvinyl alcohol resin prepared by the preparation method corresponding to the solution of the second technical problem, preferably the application in the thermoplastic processing of polyvinyl alcohol with high vinyl alcohol content.
In order to solve one of the above technical problems, the present invention provides a thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability, which may comprise the following components: sulfonic acid group copolymerized polyvinyl alcohol and a thermoplastic agent; the melting point of the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin can be 120-180 ℃, and the thermal decomposition temperature can be higher than 240 ℃.
The sulfonic acid group copolymerized polyvinyl alcohol can be one or a mixture of more of vinyl alcohol-vinyl acetate-sulfonic acid group unsaturated hydrocarbon monomer terpolymer;
preferably, the first and second electrodes are formed of a metal,
the degree of polymerization of the vinyl alcohol-vinyl acetate-sulfonic acid group unsaturated hydrocarbon monomer terpolymer can be 500 to 3500, preferably 600 to 3000, more preferably 600 to 2000, and even more preferably 800 to 1700.
The vinyl alcohol-vinyl acetate-sulfonic group unsaturated hydrocarbon monomer terpolymer has a vinyl alcohol unit content of 94-99.7 mol%, the balance of vinyl acetate and sulfonic group units, and the total content of the vinyl acetate unit and the sulfonic group units (namely the total content of the vinyl acetate unit and the sulfonic group units) can be 0.3-6 mol%; the mass fraction of sulfur element in the terpolymer can be 0.1-4%, and preferably 0.6-2.5%.
The mass ratio of the sulfonic acid group copolymerized polyvinyl alcohol to the thermoplastic agent can be (60-95) to (5-40), preferably (60-85): (15 to 40).
The sulfonic acid group copolymerized polyvinyl alcohol can be prepared by copolymerizing vinyl acetate monomers and unsaturated hydrocarbon monomers containing sulfonic acid or salt groups thereof.
The unsaturated hydrocarbon monomer containing sulfonic acid or salt group thereof can comprise at least one of olefin sulfonic acid or salt thereof, sulfonic alkyl maleate, sulfonic alkyl acrylamide, sulfonic alkyl acrylate and olefin benzene sulfonate; the unsaturated hydrocarbon comonomer containing sulfonic acid or its salt group may preferably be an olefin sulfonic acid or its salt; further preferably: the alkene sulfonic acid or the salt thereof can be at least one selected from vinyl sulfonic acid or the salt thereof, allyl sulfonic acid or the salt thereof, and methallyl sulfonic acid or the salt thereof.
The thermoplastic agent may comprise at least one of a polyol, a polyether polyol, or a polyol alcoholate;
wherein, the polyhydric alcohol can be preferably one or more than two of ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, xylitol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and tetrapropylene glycol;
the polyether polyol can be preferably one or more than two of polyethylene glycol, polypropylene glycol, polyglycerol, ethylene glycol-propylene glycol copolymer, polypropylene oxide and polytetrahydrofuran;
the polyol ester compound may preferably be one or more of ethylene glycol ester and glycerin ester compounds.
In order to solve the second technical problem, the invention provides a method for preparing the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin, which comprises the following steps:
the components including the required amount of sulfonic acid group copolymerized polyvinyl alcohol and the thermoplastic agent are melted, blended and extruded to obtain the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin.
Wherein the extrusion temperature may be 120 to 210 ℃, preferably 150 to 195 ℃, more preferably 150 to 180 ℃.
In order to solve the third technical problem, the invention provides the application of the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin or the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin prepared by the preparation method, preferably the application in the thermoplastic processing of polyvinyl alcohol with high vinyl alcohol content.
In a particular embodiment of the method of the invention,
in order to solve one of the above technical problems, the present invention provides a thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability, which may comprise the following components: sulfonic acid group copolymerized polyvinyl alcohol and a thermoplastic agent;
the melting point of the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin is 120-180 ℃, and the thermal decomposition temperature is more than 240 ℃.
Preferably, the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin has a melt index of 1 to 10g/10min (150 to 190 ℃/2.16 to 10 kg).
The sulfonic acid group copolymerized polyvinyl alcohol can be one or a mixture of more of vinyl alcohol-vinyl acetate-sulfonic acid group unsaturated hydrocarbon monomer terpolymer;
preferably, the first and second electrodes are formed of a metal,
the polymerization degree of the vinyl alcohol-vinyl acetate-sulfonic group unsaturated hydrocarbon monomer terpolymer can be 500-3500, preferably 600-3000, more preferably 600-2000, and further preferably 800-1700;
the vinyl alcohol-vinyl acetate-sulfonic acid group unsaturated hydrocarbon monomer terpolymer has a vinyl alcohol unit content of 94 to 99.7mol% (e.g., 94%, 95%, 96%, 97%, 98%, 99%, 99.1%, 99.2%, 99.3%, 99.4%, 99.5%, 99.6% or any value therebetween), a remaining portion of vinyl acetate and sulfonic acid group units, a total content of both of 0.3 to 6mol% (e.g., 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 2%, 3%, 4%, 5%, 6% or any value therebetween), and a mass fraction of sulfur element in the terpolymer of 0.1 to 4% (e.g., 0.1%, 0.3%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 3.8%, 4% or any value therebetween).
The thermoplastic agent may be selected from at least one of a polyol, a polyether polyol, or a polyol alcoholate.
The mass ratio of the sulfonic acid group co-polyvinyl alcohol to the thermoplastic agent can be (60-95) to (5-40), preferably (60-85): (15 to 40).
The sulfonic acid group copolymerized polyvinyl alcohol can be prepared by copolymerizing vinyl acetate monomers and unsaturated hydrocarbon monomers containing sulfonic acid or salt groups thereof to prepare polymers and then carrying out alcoholysis on the obtained polymers.
The copolymerization method is not particularly limited, and a known method such as solution polymerization, emulsion polymerization, suspension polymerization, or bulk polymerization can be used, and solution polymerization is preferable. The solvent used for copolymerization may be a lower alcohol such as methanol, ethanol, n-propanol, isopropanol, etc., preferably methanol. The polymerization catalyst used for the copolymerization may be a radical polymerization catalyst, for example, a known radical polymerization catalyst such as azobisisobutyronitrile, acetyl peroxide, benzoyl peroxide, etc., and azobisisobutyronitrile is preferable. The polymerization temperature depends on the solvent used and the reaction pressure, and is generally from room temperature to the boiling point of the solvent. And dissolving the obtained polymer in a sodium hydroxide methanol solution for alcoholysis, and drying and crushing to obtain the sulfonic acid group copolymerized polyvinyl alcohol used in the invention.
Preferably, the first and second electrodes are formed of a metal,
the unsaturated hydrocarbon monomer containing sulfonic acid or salt group thereof can comprise at least one of olefin sulfonic acid or salt thereof, sulfonic alkyl maleate, sulfonic alkyl acrylamide, sulfonic alkyl acrylate and olefin benzene sulfonate; further preferably: the unsaturated hydrocarbon comonomer containing sulfonic acid or its salt group may preferably be olefin sulfonic acid or its salt; further preferably: the alkene sulfonic acid or the salt thereof can be at least one selected from vinyl sulfonic acid or the salt thereof, allyl sulfonic acid or the salt thereof, and methallyl sulfonic acid or the salt thereof.
In the above technical scheme, the unsaturated hydrocarbon monomer of sulfonic acid or its salt group can be represented by the general formula X-SO 3 - Y + Wherein X represents an unsaturated hydrocarbon group such as a straight or branched chain having 1 to 20 carbon atoms or an alkenylene or alkynylene group containing a benzene ring or an amide, and Y represents a hydrogen atom or an alkali metal or ammonium group. Examples thereof include olefin sulfonic acid or a salt thereof, sulfonic acid alkyl maleate, sulfonic acid alkyl acrylamide, sulfonic acid alkyl acrylate, olefin benzenesulfonic acid; further preferably an olefin sulfonic acid or a salt thereof; more preferably at least one of vinylsulfonic acid or a salt thereof, allylsulfonic acid or a salt thereof, and methallylsulfonic acid or a salt thereof.
In the above embodiment, the thermoplastic agent may comprise at least one of a polyol, a polyether polyol, or a polyol alcoholate;
wherein, the first and the second end of the pipe are connected with each other,
the polyhydric alcohol can be preferably one or more than two of ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, xylitol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and tetrapropylene glycol;
the polyether polyol can be preferably one or more than two of polyethylene glycol, polypropylene glycol, polyglycerol, ethylene glycol-propylene glycol copolymer, polypropylene oxide and polytetrahydrofuran;
the polyol ester compound may preferably be one or more of ethylene glycol ester and glycerin ester compounds.
The thermoplastic agent more preferably contains at least one of ethylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, and xylitol; the thermoplastic agent is more preferably at least one of glycerol and pentaerythritol, sorbitol, xylitol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, polyethylene glycol, and polyglycerol; wherein the mass content of the glycerol is more than or equal to 50 percent (for example, the mass content can be more than or equal to 60 percent, more than or equal to 70 percent, more than or equal to 80 percent, more than or equal to 90 percent, more than or equal to 92 percent and the like).
In order to solve the second technical problem, the invention provides a method for preparing the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin, which comprises the following steps:
the components including the required amount of sulfonic acid group copolymerized polyvinyl alcohol and the thermoplastic agent are melted, blended and extruded to obtain the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin. Specifically, the required amount of components including the sulfonic acid group copolymerized polyvinyl alcohol and the thermoplastic agent are added into a double-screw extruder, and the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin is obtained through melting, kneading, extruding, cooling and granulating.
In the above technical scheme, the preparation method of the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol can be a twin-screw continuous melt blending extrusion method, preferably, dry sulfonic acid group copolymerized polyvinyl alcohol and thermoplastic agent are blended according to a required proportion and then added into a twin-screw extruder for melting, kneading, extruding, cooling and granulating to obtain the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol; more preferably: and respectively and directly adding the dried sulfonic acid group copolymerized polyvinyl alcohol and the thermoplastic agent into a double-screw extruder according to the required proportion for melting, kneading, extruding, cooling and granulating to obtain the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol.
Wherein, the first and the second end of the pipe are connected with each other,
the extrusion temperature of the double-screw extruder can be 120-210 ℃, preferably 150-195 ℃, and more preferably 150-180 ℃; the screw speed may be from 50 to 400rpm, preferably from 150 to 300rpm.
The mass fraction of sulfur element in the sulfonic acid group copolymerized polyvinyl alcohol resin used in the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin is 0.1-4%, preferably 0.6-2.5%. If the content of the sulfur element is too low, the thermoplastic processing is difficult, the melting point is high, the thermal decomposition temperature is low, and the processing window is narrow; if the content is too high, the properties of the polyvinyl alcohol having a high vinyl alcohol content, such as poor water solubility and poor oxygen barrier property, cannot be maintained.
The third purpose of the invention is to provide the application of the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin or the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin prepared by the preparation method, preferably the application in the thermoplastic processing of polyvinyl alcohol with high vinyl alcohol content.
Compared with the prior art, the invention has the following positive effects:
1. the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin realizes thermoplastic processing under the condition that the vinyl alcohol content is up to 94-99.7 mol%, the melting point of the resin is as low as 120-180 ℃, the thermal decomposition temperature is more than 240 ℃, and the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin has a wide processing window.
2. The thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin has the melt index of 1-10 g/10min (150-190 ℃/2.16-10 kg), is colorless and transparent, and has good processing fluidity.
3. The thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin does not contain soft water in the formula, and has high thermoplastic processing stability.
4. The invention does not need to mix all components in advance, and all components can be added into the double-screw extruder through different feeders simultaneously, so that the production process is simpler.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.
Sources of feedstock for the present application
The sulfonic acid group-copolymerized polyvinyl alcohol can be prepared by referring to a published graduation paper (Jiminghui. Polyvinyl alcohol copolymerization modification [ D ]. Donghua university, 2003.) and a similar synthetic method. The preparation method of the sulfonic acid group copolymerized polyvinyl alcohol resin comprises the following steps: vinyl acetate, sodium allylsulfonate methanol solution and methanol (the mass ratio of the solvent to the monomer is 0.5. Introducing nitrogen for protection, heating to 60 ℃ while stirring, adding azodiisobutyronitrile methanol solution to initiate polymerization reaction, controlling the reaction temperature to be 60-62 ℃, polymerizing for 1-2 h, then adding the residual sodium allylsulfonate methanol solution, and continuing to polymerize for 1-2 h to obtain the copolymer. Unreacted vinyl acetate monomer was removed with methanol vapor using a vapor distillation apparatus. Purifying the copolymer, adding sodium hydroxide methanol solution, heating in water bath at 35-45 deg.c for alcoholysis while stirring for 10-30 min, drying and crushing to obtain sulfo group copolymerized polyvinyl alcohol, and determining the sulfur content in the copolymer via element analysis to determine the actual copolymerization proportion of the sulfo group modifying unit. Controlling the molar ratio of the vinyl acetate to the sodium allylsulfonate in the polymerization reaction to be (90-99): (1-10) and the proportion of sodium hydroxide methanol solution in alcoholysis reaction (the molar ratio of sodium hydroxide to vinyl acetate structural unit is 0.007-0.01) to obtain the sulfonic acid group copolymerized polyvinyl alcohol resin with different sulfur contents and different vinyl alcohol contents.
The invention carries out performance measurement according to the following method:
elemental analysis test: the content of sulfur in the sulfonic acid group copolymerized polyvinyl alcohol was measured by using a Flash2000 type elemental analyzer of Saimer Feishale, USA, according to SN/T3005-2011. 2-3 mg of sample, the CHNS mode is selected by the instrument, the carrier gas and the reference gas are helium, the flow rates are 140ml/min and 100ml/min respectively, the combustion column temperature is 950 ℃, and the detection chromatographic column temperature is 65 ℃.
Differential Scanning Calorimetry (DSC) test: the measurement was carried out using a Discovery differential scanning calorimeter from TA in the USA in accordance with ISO 11357-2016. 5-10 mg of sample, nitrogen atmosphere, and 50mL/min of flow. The test procedure was as follows: heating from 40 deg.C to 220 deg.C, holding the temperature for 1min, cooling to-50 deg.C, holding the temperature for 1min, and heating to 220 deg.C at a heating/cooling rate of 10 deg.C/min. The second temperature rise was recorded and the melting point of the sample was analyzed using the instrument suite analysis software, tai instruments trios version 3.1.5.
Thermogravimetric analysis (TG) test: the thermal stability of the samples was examined using a thermo-gravimetric analyzer model TGA2 STAReStatem, mettlerToledo, switzerland, at a flow rate of 50mL/min, at a rate of 10 deg.C/min, from 40 deg.C to 700 deg.C under a nitrogen atmosphere.
Melt index testing: the melt index is measured according to ISO1133-2011 by using a CEASTMF20 type melt index meter of Instron corporation in America, the temperature of a cylinder is 150-190 ℃, the load is 2.16-10 kg, the diameter of a die is 2.095mm, the length is 8mm, and the preheating time is 4min.
[ example 1 ] A method for producing a polycarbonate
The polymerization degree of the sulfonic acid group copolymerized polyvinyl alcohol resin is 1000, the unit content of vinyl alcohol is 95mol%, the total content of vinyl acetate and sodium allylsulfonate is 5mol%, the mass fraction of sulfur element is 0.7%, and the sulfonic acid group copolymerized polyvinyl alcohol resin is prepared by PolyLabHAAKE of ThermoFisher science and technology company in America TM RheomexOSPTW16 co-rotating twin-screw extruder (screw diameter 16mm, L/D = 40) was subjected to thermoplasticity, extrusion, cooling, and pelletization. The extruder has 11 sections from the feeding port to the die, which are numbered as 1-11, wherein the section 1 only plays a role of feeding and can not be heated. And a powder feeder attached to the extruder is used for feeding the sulfonic acid group copolymerized polyvinyl alcohol raw material into the double screw after calibration, and the feeding speed is 800g/h. The thermoplastic agent (the thermoplastic agent is a mixture containing 98% of glycerin and 2% of diethylene glycol by mass fraction) is added into the extruder through a feed port, and the feeding speed is 200g/h. The temperatures of 2-11 sections of the extruder are respectively as follows: 160 ℃,170 ℃,180 ℃,180 ℃,180 ℃,180 ℃,180 ℃,180 ℃,180 ℃ and 170 ℃, with the screw speed set at 200rpm. The extruder is provided with a circular neck ring with the diameter of 3mm, and a sample strip is extruded from the neck ring, cooled by air and granulated by a granulator to prepare the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin.
The obtained resin has smooth surface, uniform thickness, melting point of 164 deg.C, thermal decomposition temperature of 249 deg.C, and melt index of 1g/10min (180 deg.C/10 kg).
[ example 2 ] A method for producing a polycarbonate
The process of example 1 was followed except that the feeding rate of the sulfonic acid group-copolymerized polyvinyl alcohol material was 600 g/hr and the feeding rate of the thermoplastic agent was 400 g/hr.
The obtained resin has smooth surface, uniform thickness, melting point of 159 deg.C, thermal decomposition temperature of 242 deg.C, and melt index of 2.1g/10min (180 deg.C/2.16 kg).
[ example 3 ]
According to the method described in example 1, except that the polymerization degree of the sulfonic acid group copolymerized polyvinyl alcohol resin used was 1000, the content of vinyl alcohol units was 95mol%, the total content of vinyl acetate and sodium allylsulfonate units was 5mol%, the mass fraction of sulfur element was 1%, the feeding speed of the sulfonic acid group copolymerized polyvinyl alcohol raw material was 700g/h, and the feeding speed of the thermoplastic agent was 300g/h. The temperatures of 2-11 sections of the extruder are respectively as follows: 170 ℃,180 ℃,190 ℃,190 ℃,190 ℃,190 ℃ and 180 ℃, and the screw rotation speed is set at 250rpm.
The obtained resin has smooth surface, uniform thickness, melting point of 170 deg.C, thermal decomposition temperature of 241 deg.C, and melt index of 2.2g/10min (180 deg.C/2.16 kg).
[ example 4 ]
According to the method described in example 1, except that the polymerization degree of the sulfonic acid group copolymerized polyvinyl alcohol resin used was 1000, the content of vinyl alcohol units was 95mol%, the total content of vinyl acetate and sodium allylsulfonate units was 5mol%, the mass fraction of sulfur element was 1.6%, the feeding speed of the sulfonic acid group copolymerized polyvinyl alcohol raw material was 750g/h, and the feeding speed of the thermoplastic agent was 250g/h. The temperatures of 2-11 sections of the extruder are respectively as follows: 170 ℃,180 ℃,190 ℃,190 ℃,190 ℃,190 ℃,180 ℃ and the screw rotation speed is set at 250rpm.
The obtained resin has smooth surface, uniform thickness, melting point of 172 deg.C, thermal decomposition temperature of 244 deg.C, and melt index of 3.9g/10min (180 deg.C/10 kg).
[ example 5 ]
The process of example 1 was followed, except that the sulfonic acid group-copolymerized polyvinyl alcohol resin used had a polymerization degree of 1000, a vinyl alcohol unit content of 97mol%, a total content of vinyl acetate and sodium allylsulfonate units of 3mol%, a mass fraction of sulfur element of 1%, a feeding rate of the raw material of the sulfonic acid group-copolymerized polyvinyl alcohol of 700g/h, and a feeding rate of the thermoplastic agent (a mixture of the thermoplastic agent in terms of mass fraction, containing 95% glycerin, 5% dipropylene glycol) of 300g/h. The temperatures of 2-11 sections of the extruder are respectively as follows: 175 ℃,185 ℃,195 ℃,195 ℃,195 ℃,195 ℃ and 185 ℃ and the screw speed was set at 250rpm.
The obtained resin has smooth surface, uniform thickness, melting point of 173 deg.C, thermal decomposition temperature of 245 deg.C, and melt index of 2.1g/10min (190 deg.C/2.16 kg).
[ COMPARATIVE EXAMPLE 1 ]
According to the method described in example 1, except that a polyvinyl alcohol resin having a polymerization degree of 1000, a vinyl alcohol unit content of 95mol% and a vinyl acetate unit content of 5mol% and containing no sulfonic acid group-copolymerized modifying group was used.
The obtained resin has rough appearance, granular feeling with crystal points, uneven thickness and poor striping property, and cannot be processed by hot molding.
[ COMPARATIVE EXAMPLE 2 ]
According to the method described in example 2, except that a polyvinyl alcohol resin having a polymerization degree of 1000, a vinyl alcohol unit content of 95mol% and a vinyl acetate unit content of 5mol% and containing no sulfonic acid group-copolymerized modifying group was used.
The obtained resin had a slightly rough surface, slightly uneven thickness, poor stability in continuous granulation, a melting point of 186 ℃ and a thermal decomposition temperature of 203 ℃ and a melt index could not be measured (180 ℃/2.16 kg).
[ COMPARATIVE EXAMPLE 3 ]
According to the method described in example 1, except that the sulfonic acid group-copolymerized polyvinyl alcohol used had a degree of polymerization of 1000, a content of vinyl alcohol units of 95mol%, a total content of vinyl acetate and sodium allylsulfonate units of 5mol%, and a mass fraction of sulfur element of 0.08%.
The obtained resin has slightly rough surface and uniform thickness, can be continuously granulated, has the melting point of 190 ℃, the thermal decomposition temperature of 210 ℃ and the melt index which cannot be measured (180 ℃/10 kg).
[ COMPARATIVE EXAMPLE 4 ]
The process described in example 1 is followed, except that the thermoplastic used contains soft water (the thermoplastic is a mixture of 80% glycerol and 20% soft water by mass).
The obtained resin has the defects of air bubbles, holes and the like, the preparation process is unstable, and the fluctuation of the melting point, the thermal decomposition temperature and the melt index of the particles is large.
[ COMPARATIVE EXAMPLE 5 ]
The method as described in example 5 was conducted except that a polyvinyl alcohol resin having a polymerization degree of 1000, a vinyl alcohol unit content of 97mol% and a vinyl acetate unit content of 3mol% was used, and no sulfonic acid group-copolymerized modifying group was contained.
The resin had a slightly rough surface, slightly varied thickness, and poor stability in continuous granulation, a melting point of 192 ℃ and a thermal decomposition temperature of 207 ℃ and a melt index of 190 ℃/2.16kg could not be measured.
Claims (10)
1. A thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin with low melting point and high thermal stability comprises the following components: sulfonic acid group polyvinyl alcohol copolymer and thermoplastic agent;
the melting point of the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin is 120-180 ℃, and the thermal decomposition temperature is more than 240 ℃.
2. The thermoplastic sulfonic acid group-copolymerized polyvinyl alcohol resin according to claim 1, wherein:
the sulfonic acid group copolymerized polyvinyl alcohol is one or a mixture of more of vinyl alcohol-vinyl acetate-sulfonic acid group unsaturated hydrocarbon monomer terpolymer;
preferably, the first and second electrodes are formed of a metal,
the polymerization degree of the vinyl alcohol-vinyl acetate-sulfonic group unsaturated hydrocarbon monomer terpolymer is 500-3500, preferably 600-3000.
3. The thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin according to claim 2, wherein:
the vinyl alcohol-vinyl acetate-sulfonic group unsaturated hydrocarbon monomer terpolymer contains 94-99.7 mol% of vinyl alcohol units, the balance is vinyl acetate and sulfonic group units, and the total content of the vinyl alcohol-vinyl acetate-sulfonic group unsaturated hydrocarbon monomer terpolymer and the vinyl acetate-sulfonic group unsaturated hydrocarbon monomer is 0.3-6 mol%; the mass fraction of sulfur element in the terpolymer is 0.1-4%, preferably 0.6-2.5%.
4. The thermoplastic sulfonic acid-based copolymerized polyvinyl alcohol resin according to claim 1, wherein:
the thermoplastic agent is selected from at least one of polyol, polyether polyol or polyol alcoholate;
wherein the content of the first and second substances,
the polyalcohol is preferably one or more of ethylene glycol, propylene glycol, glycerol, pentaerythritol, sorbitol, mannitol, xylitol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol and tetrapropylene glycol;
the polyether polyol is preferably one or more of polyethylene glycol, polypropylene glycol, polyglycerol, ethylene glycol-propylene glycol copolymer, polypropylene oxide and polytetrahydrofuran;
the polyol ester compound is preferably one or more than two of glycol ester and glyceride compounds.
5. The thermoplastic sulfonic acid group-copolymerized polyvinyl alcohol resin according to claim 1, wherein:
the mass ratio of the sulfonic acid group copolymerized polyvinyl alcohol to the thermoplastic agent is (60-95) to (5-40), preferably (60-85): (15 to 40).
6. The thermoplastic sulfonic acid group-copolymerized polyvinyl alcohol resin according to claim 1, wherein:
the sulfonic acid group copolymerized polyvinyl alcohol is prepared by copolymerizing vinyl acetate monomers and unsaturated hydrocarbon monomers containing sulfonic acid or salt groups thereof.
7. The thermoplastic sulfonic acid group-copolymerized polyvinyl alcohol resin according to claim 6, wherein:
the unsaturated hydrocarbon monomer containing sulfonic acid or the salt group thereof comprises at least one of olefin sulfonic acid or salt thereof, sulfonic alkyl maleate, sulfonic alkyl acrylamide, sulfonic alkyl acrylate and olefin benzene sulfonate; preferably: the unsaturated hydrocarbon comonomer containing sulfonic acid or a salt group thereof is preferably alkene sulfonic acid or a salt thereof; further preferably: the alkene sulfonic acid or the salt thereof is at least one of vinyl sulfonic acid or the salt thereof, allyl sulfonic acid or the salt thereof and methallyl sulfonic acid or the salt thereof.
8. The method for producing a thermoplastic sulfonic acid group-copolymerized polyvinyl alcohol resin according to any one of claims 1 to 7, characterized by comprising the steps of:
the components including the required amount of sulfonic acid group copolymerized polyvinyl alcohol and the thermoplastic agent are melted, blended and extruded to obtain the thermoplastic sulfonic acid group copolymerized polyvinyl alcohol resin.
9. The method for preparing a thermoplastic sulfonic acid-based copolymerized polyvinyl alcohol resin according to claim 8, wherein:
the extrusion temperature is 120 to 210 ℃, preferably 150 to 195 ℃.
10. Use of the thermoplastic sulfonic acid group-copolymerized polyvinyl alcohol resin according to any one of claims 1 to 7 or the thermoplastic sulfonic acid group-copolymerized polyvinyl alcohol resin prepared by the preparation method according to claim 8 or 9, preferably in thermoplastic processing of polyvinyl alcohol having a high vinyl alcohol content.
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