CN102391598B - Polyvinyl alcohol material and production method thereof - Google Patents
Polyvinyl alcohol material and production method thereof Download PDFInfo
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- CN102391598B CN102391598B CN2011102642057A CN201110264205A CN102391598B CN 102391598 B CN102391598 B CN 102391598B CN 2011102642057 A CN2011102642057 A CN 2011102642057A CN 201110264205 A CN201110264205 A CN 201110264205A CN 102391598 B CN102391598 B CN 102391598B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92885—Screw or gear
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Abstract
The invention provides a polyvinyl alcohol material and a production method thereof. The polyvinyl alcohol material is prepared from a composition which comprises the following components in part by weight: 30 to 60 parts of polyvinyl alcohol powder, 10 to 60 parts of plasticizer, 0.1 to 5 parts of heat stabilizer, and 0.1 to 3.5 parts of melt modifier. The production method comprises the following steps of: blending the polyvinyl alcohol powder and the plasticizer; extruding a mixture by using a double-screw extruder, and dicing into grains; mixing the grains, the heat stabilizer, and the melt modifier to obtain a uniform mixed material; and extruding the mixed material by using the double-screw extruder to obtain composition melt, and allowing the composition melt to flow through a melt pressure stabilization system and then directly flow into a casting mould or a sheet mould to obtain a polyvinyl alcohol film or sheet. The polyvinyl alcohol product which is produced by the method has a bright, clean and smooth surface and good mechanical property and high transparency.
Description
Technical field
The present invention relates to a kind of polyvinyl alcohol material and production method thereof.
Background technology
Have great amount of hydroxy group on the molecular chain of polyvinyl alcohol (PVA), have solubilized and biodegradable environmental friendliness characteristic.Therefore its goods film article especially except having preferably mechanical property, also has high oil-proofness, high transparent and to the performance of some special excellences such as high barrier of oxygen etc.Therefore, polyvinyl alcohol replaces now nondegradable polyolefine as wrapping material and some otherly has the property material and have incomparable advantage.Although the polyvinyl alcohol advantage is obvious, but owing to containing a large amount of polarity hydroxyls on its molecular chain, molecular structure is regular, melt temperature equals even higher than decomposition temperature, especially its thermostability sharply descends under the condition that high temperature (greater than 100 ℃) aerobic exists, decompose rapidly, therefore polyvinyl alcohol is difficult to carry out thermoplastic machine-shaping for many years.
In order to overcome the shortcoming of PVA pyrolytic decomposition, the PVA solution coat method that the production method of PVA (PVOH) FILM generally has (1) to have water to participate in.(2) the PVA extrusion by melting of anhydrous participation.Wherein, method (1) is that polyvinyl alcohol is water-soluble, add other components such as certain releasing agent and tensio-active agent, linking agent etc., with coating or the method for swing roller, certain density polyvinyl alcohol solution is transferred on stainless steel shaft, then the film forming of progressively dewatering.More patent report this PVA thin film technology method.This method advantage is that PVA is processed at lower temperature, has avoided the PVA thermolysis, but its production unit is complicated, technical process is long, especially in the water smoking, consumes a large amount of heat energy, although it is eco-friendly producing the PVA film, its production process is not eco-friendly.In recent years, many investigators attempt PVA is carried out fusion plastification processing, it is above-mentioned PVA production method (2), the method of main report has two kinds: the fusing point that (a) reduces PVA under the condition that water exists, make its Blown Film at lower temperature, but unstable in the PVA system of water, not every water molecules can advance in the PVA molecule in plasticising, the water molecules that overflows (140-220 ℃) at the production temperature of its report usually produces abscess, can not continuous and stable production (CN200380103342.6).The another kind of report method of PVA melt-processed is that (b) is under anhydrous condition, adopt alcamines, amides small molecules to make softening agent, make PVA melt extrude processing, this method is with the production of alcoholysis degree greater than 88% PVA, but the pyrolytic decomposition of PVA is affected the permanent stability of its production.The polyvinyl alcohol molecule structure of high alcoholysis degree is more regular, fusing point is higher, for example the polymerization degree be the fusing point of 1700 PVA up to 235 ℃, PVA at so high temperature hot melt processing hardly may, therefore the melt-processed of the PVA of high alcoholysis degree is the difficult point of research always.
In sum, the coating method power consumption that has water to participate in is large, and production efficiency is low, and the high but production stability of extrusion by melting production efficiency can not guarantee.Therefore it is desirable to provide a kind of method can avoid polyvinyl alcohol to decompose at lower temperature as far as possible, can adopt again the production of the large high alcoholysis degree PVA (PVOH) FILM of the high-efficiency method for producing stably manufactured, the especially production difficulty that melt extrude simultaneously.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of polyvinyl alcohol material and production method thereof of being produced by high alcoholysis degree polyvinyl alcohol compositions, adopt this polyvinyl alcohol compositions and production method, can realize that the stable of high alcoholysis degree PVA (PVOH) FILM or sheet material melt extrudes and moulding.
The invention provides a kind of polyvinyl alcohol material, it is made by the composition that comprises following component: polyvinyl alcohol powder 30～60 weight parts, preferred 40～60 weight parts; Softening agent 10～60 weight parts, preferred 20～50 weight parts; Thermo-stabilizer 0.1～5 weight part, preferred 0.2～3 weight part; Melt modification agent 0.1～3.5 weight part, preferred 0.2～2 weight part.
According to polyvinyl alcohol material provided by the invention, wherein, the polymerization degree of described polyvinyl alcohol can be 500～2000, preferred 1700～2000.Preferably, the alcoholysis degree of described polyvinyl alcohol is 88～99.9%, more preferably 98～99.9%.The molecular weight of the polyvinyl alcohol that the present invention is used can be 60000～110000, is preferably 80000～110000.The viscosity of the higher melting method of molecular weight is larger, more easily degraded during high temperature, and melt-processed is more difficult.Therefore the present invention is according to different polyvinyl alcohol molecule amounts, all adopts different measuring in softening agent and thermo-stabilizer.For example, low-molecular-weight polyvinyl alcohol has removing of acetic acid molecule in the plasticising process, can be aided with acid absorber to reduce the degraded of PVA, guarantees the quality of film; The polyvinyl alcohol of high molecular is because Intermolecular Forces is stronger, easily degraded in the course of processing, the thermo-stabilizer content that therefore can add is many than low alcoholysis level PVA's, thermo-stabilizer content increase the increase that can cause melt viscosity, can add a certain amount of lubricant for easy to process.Concrete grammar will embody in an embodiment.
Polyvinyl alcohol powder as raw material of the present invention can be the various PVA raw materials that are purchased, such as the PVA product that can think that Sichuan vinylon plant, Anhui vinylon plant, Japanese kurary company, U.S. celanese company etc. produce.
According to polyvinyl alcohol material provided by the invention, wherein, it is water that described softening agent has a component at least.In multiple embodiments of the present invention, described softening agent is in one or more and/or following material in water and following material two kinds or more than the mixture of two kinds of reaction product under water exists: C2～C8 polyvalent alcohol, C3～C15 ester, C3～C15 ether, C3～C15 amine and C3～C15 epoxy compounds.That is to say, beyond dewatering, softening agent of the present invention can also contain one or more in above-mentioned substance, perhaps two kinds in above-mentioned substance or more than two kinds of reaction product under water exists.
Preferably, described softening agent is in one or more and/or following material in water and following material two kinds or more than the mixture of two kinds of reaction product under water exists: ethylene glycol, glycerol, tetramethylolmethane, neopentyl glycol, sorbyl alcohol, glycol ether, triglycol, molecular weight are 200～1000 polyoxyethylene glycol, TriMethylolPropane(TMP), diethanolamine, trolamine, triethylene tetramine, oxyethane, propylene oxide, 1-methyl propylene oxide, 1-butyl butylene oxide ring.More preferably, described softening agent comprise propylene oxide and sorbyl alcohol under water exists reaction product or TriMethylolPropane(TMP) under water exists with the reaction product of diethanolamine and propylene oxide, its content is 5～50% of softening agent gross weight, is preferably 10～30%.In some preferred embodiments, in described softening agent, the content of water is 20～90% of softening agent gross weight, and preferably, the content of water in described composition is 40～60% of composition total weight.Preferably, described C2～C8 polyvalent alcohol, C3～C15 amine and their reaction product account for 10～30% of softening agent gross weight.
In a kind of specific embodiment, the reaction process of a kind of component of preparation softening agent is as follows: 5～20 % by weight of tetramethylolmethane with water are added to the water, under the reflux cooling condition, take the mol ratio tetramethylolmethane: propylene oxide adds propylene oxide as 1: 2～5 amount, reacted under 20～80 ℃ 1～5 hour, preferred reaction 1～3 hour, cooling rear discharging can obtain propylene oxide and the reaction product of tetramethylolmethane under water exists.
In another kind of specific embodiment, the method of a kind of component of preparation softening agent is: C2～C8 polyvalent alcohol and C3～C15 amine are added to the water with 10～30% of softening agent gross weight, wherein, the mol ratio of C2-C8 polyvalent alcohol and C3-C15 amine can be 10～20: 1; To be that 1: 2～5 oxyethane adds with total amount (total amount of C2-C8 polyvalent alcohol and the addition of C3-C15 amine mole number) mol ratios both, will react after product and water together as softening agent.
Table 1 has been listed PVA117 and has been added plasticizing data before and after softening agent.As can be seen from Table 1, after adding softening agent, the fusing point of plasticizing PVA all decreases with respect to pure PVA, illustrates that plasticizer of the present invention adds the rear remarkable fusing point that reduces PVA, makes process window T
f～T
mIncrease (T
fBe decomposition temperature, T
mBe fusing point), make PVA have the performance of thermoplastic processing, Tc (T
p) and degree of crystallinity (X
c) also purer PVA decrease, illustrate and destroyed the original height ordered structure of PVA adding of softening agent, and then reduced Intermolecular Forces, mobility is strengthened.And in softening agent, the simple increase of any component all can cause the decline of degree of crystallinity and Tc.Therefore, softening agent of the present invention can be realized the melt-processed of high alcoholysis degree PVA.
Table 1
According to polyvinyl alcohol material provided by the invention, wherein, described thermo-stabilizer can be the thermo-stabilizer of this area routine.For example, can be one or more in free radical absorption agent, free radical stabilizer, lubricant and active substance absorption agent.In a kind of preferred embodiment, described free radical absorption agent can comprise main absorption agent and absorbefacient, and main absorption agent can comprise alkylphenol compounds, alkylidene group phenolic compound, alkyl bisphenol compound, hydroxy phenyl acrylic ester compound, aminophenols, thiobisphenol compounds or its combination.Absorbefacient comprises hydroxy ester compounds, saturated acid ester compound, monothioester compounds, inferior phosphide compounds or its combination.Organic ester salt, cyclohexadione compounds and organo-metallic salt or its combination that described free radical stabilizer can comprise organic salt that the metals such as Ca, Ba, Sn form, be formed by Zn or Cd etc.Described lubricant can comprise hydro carbons lubricant such as solid paraffin, whiteruss, fatty acid such as stearic acid, ricinolic acid, aliphatic amide type and ester class, as stearylamide, butyl stearate, stearin, and metal soap, as one or more in Zinic stearas, barium stearate, calcium stearate.Described active substance absorption agent can comprise combination, mineral alkali and/or inorganic salt and the combination of many methylol compounds and the combination of above-mentioned substance or combination and Nano compound of mineral alkali, inorganic salt, mineral alkali and inorganic salt.under preferable case, the thermo-stabilizer that the present invention uses can be alkylphenol compounds, the alkylidene group phenolic compound, the alkyl bisphenol compound, the hydroxy phenyl acrylic ester compound, aminophenols, the thiobisphenol compounds, the hydroxy ester compounds, the saturated acid ester compound, the monothioester compounds, inferior phosphide compounds, sulfo-glycolic acid alkyl ester tin octylate, mercaptan propionic ester butyl tin, mercaptan acetic ester tin octylate, barium stearate, calcium stearate, Zinic stearas, dibasic lead phosphite, dibasic lead stearate, tribasic lead sulfate, 1, one or more in the 3-cyclohexadione compounds, be preferably alkylphenol compounds, the thiobisphenol compounds, the monothioester compounds, inferior phosphide compounds, one or more in barium stearate and calcium stearate.Particularly, it is thermo-stabilizer described in 200810180879.7 patent application that the thermo-stabilizer that the present invention uses can be preferably application number, and it is incorporated herein by reference in full.
According to polyvinyl alcohol material provided by the invention, wherein, described melt modification agent can be one or more in nano silicon, nano hydrotalcite, nano imvite and nanometer china clay, preferably, the particle diameter of described melt modification agent for example, can be 5000 orders less than 2500 orders.
The present invention also provides the production method of above-mentioned polyvinyl alcohol material, comprises the steps:
(1) blend in mixing tank with polyvinyl alcohol powder and softening agent;
(2) blend that step (1) is obtained with twin screw extruder extrude, pelletizing obtains pellet;
(3) pellet that step (2) is obtained mixes in mixing tank with thermo-stabilizer and melt modification agent, obtains uniform mixture, and airtight placement 24～96 hours, preferred 24～72 hours;
(4) mixture that step (3) is obtained is extruded with twin screw extruder and is obtained the composition melt, makes the said composition melt-flow flow directly into the casting films tool after the voltage stabilizing of melt voltage-stabilizing system or sheet die obtains PVA (PVOH) FILM or sheet material;
Wherein, alternatively, above-mentioned steps (3), (4) are following step (3 '): the pellet that step (2) is obtained obtains the composition melt with directly extruding through twin screw extruder after thermo-stabilizer and melt modification agent mix in mixing tank, makes the said composition melt-flow flow directly into the casting films tool after the voltage stabilizing of melt voltage-stabilizing system or sheet die obtains PVA (PVOH) FILM or sheet material.
According to production method provided by the invention, wherein, in step (1), the temperature of blend can be 30～150 ℃, is preferably 50～130 ℃, and the time of blend can be 10～60min, is preferably 20～50min.
According to production method provided by the invention, wherein, the length-to-diameter ratio of the twin screw extruder in described step (2) can be 28～48: 1, and diameter can be 30～65mm, and is preferably the parallel equidirectional two-screw forcing machine.The condition of extruding comprises: temperature can be 150～250 ℃, preferred 170～240 ℃; Rotating speed can be 30～200rpm.Under preferable case, the particle diameter of the pellet that is obtained by step (2) is 0.1～0.8mm.For example, a kind of preferred embodiment in, under slight shock conditions, 20 kilograms of pellets in 5min gross weight approximately 95% can pass through 25 purpose screen clothes, gross weight approximately 99% can pass through 20 purpose screen clothes.
According to production method provided by the invention, wherein, the temperature of mixing in step (3) and (3 ') can be 15～40 ℃, and the time of mixing can be 20～60min.Under preferable case, in step (3), the temperature of airtight placement should not higher than 40 ℃, for example, can be 15～40 ℃.
According to production method provided by the invention, wherein, the length-to-diameter ratio of the twin screw extruder in described step (4) can be 30～50: 1, and diameter can be 45～90mm, and is preferably the parallel equidirectional two-screw forcing machine.The condition of extruding comprises: temperature can be 40～200 ℃, preferred 50～180 ℃; Rotating speed can be 50～150rpm.The length-to-diameter ratio of the twin screw extruder in described step (3 ') can be 28～48: 1, and diameter can be 45～90mm, and the condition of extruding comprises: temperature can be 150～250 ℃, preferred 170～240 ℃; Rotating speed can be 50～150rpm.
In accordance with the present production process, in order to make the polyvinyl alcohol material performance that makes more stable, under preferable case, described step (4) and/or step (3 ') can also be included in the process of extruding with twin screw extruder, extract the unreacted softening agent of part out with vacuum system, preferably, the amount of the softening agent of extraction is 10～30% of softening agent gross weight.Under preferable case, the content of described composition melt polyvinyl alcohol when entering voltage-stabilizing system is 60～80% of composition total weight.
According to production method provided by the invention, wherein, when for the production of PVA (PVOH) FILM, in order further to improve the stability of material, this production method can also be included in step (4) and/or step (3 ') is carried out Infrared Heating to the PVA (PVOH) FILM that obtains afterwards, the temperature of heating is preferably 20～60 ℃, and the time of heating is preferably 0.5～5min.Under preferable case, carrying out Infrared Heating, to make the water ratio of described PVA (PVOH) FILM be 7～11 % by weight.
By composition of the present invention, the polyvinyl alcohol material any surface finish of producing by method of the present invention, level and smooth has good mechanical property and the transparency.
Description of drawings
Below, describe by reference to the accompanying drawings embodiment of the present invention in detail, wherein:
Fig. 1 is the melting curve of the PVA pellet that makes of embodiment 1;
Fig. 2 is the melting curve of the PVA pellet that makes of embodiment 2;
Fig. 3 is the melting curve of the PVA pellet that makes of embodiment 3.
Embodiment
Below in conjunction with embodiment, the present invention is further described in detail, the embodiment that provides is only in order to illustrate the present invention, rather than in order to limit the scope of the invention.
The raw material that the present embodiment is used:
(1) blend in mixing tank with polyvinyl alcohol powder and fluidizer, blending temperature is 60 ℃, the time is 30min;
(2) blend that step (1) is obtained with twin screw extruder extrude, pelletizing obtains pellet, the length-to-diameter ratio of twin screw extruder is 30: 1, diameter is 30mm, rotating speed 100rpm, it is as shown in table 1 that each distinguishes processing temperature:
Table 1
| Section | Charging zone | 2nd district | 3rd district | 4th district | 5th district | Head |
| Temperature/℃ | 170 | 180 | 210 | 210 | 210 | 200 |
In nitrogen atmosphere, be warming up to 240 ℃ from 0 ℃ of speed with 20 ℃/min, record the melting curve (DSC curve) of described pellet, as shown in Figure 1.Can find out from its DSC curve, the fusing point of PVA obviously reduces greatly about 135 ℃, and the workability of this explanation PVA strengthens, and is beneficial to its melt-processed.
(3) pellet that step (2) is obtained mixes in mixing tank with thermo-stabilizer and melt modification agent, 20 ℃ of mixing temperatures, and time 20min obtains uniform mixture, and airtight placement 48 hours under 40 ℃;
(4) mixture that step (3) is obtained is extruded with twin screw extruder and is obtained the composition melt, the twin screw length-to-diameter ratio is 50: 1, diameter 90mm, rotating speed 120rpm makes the said composition melt-flow flow directly into casting mold after the melt voltage-stabilizing system and obtains PVA (PVOH) FILM.The temperature of twin screw extruder sees Table 2:
Table 2
| Section | Charging zone | 2nd district | 3rd district | 4th district | 5th district | Head |
| Temperature/℃ | 80 | 100 | 130 | 130 | 130 | 120 |
(5) step (4) gained PVA (PVOH) FILM is removed moisture with the Infrared Heating method, temperature 50 C, and time 3min obtains PVA (PVOH) FILM.
Measure tensile strength and elongation at break according to GB GB/T1040.3-2006, draw speed 20mm/min, the tensile strength of gained film is 17.29Mpa, elongation at break is 267.45%.
Utilize WG7-S transmittance/mist degree determinator to measure.WG7-S transmittance/mist degree determinator is according to the GB2410-80 design, adopts microcomputer automatic operation display transparent rate and haze value simultaneously, and the mist degree of gained film is 5, and transparence is 92, illustrates that the light transmission of film is good.
With film tester for water ratio RS232, Guangzhou moral titanium electronics technology company limited.The water ratio of measuring film is 8.5%.
The raw material that the present embodiment is used:
Preparation process:
(1) blend in mixing tank with polyvinyl alcohol powder and fluidizer, blending temperature is 70 ℃, time is 30min, wherein the preparation method of fluidizer sorbyl alcohol and propylene oxide reactant in water is: 20 % by weight of sorbyl alcohol with water are added to the water, under the reflux cooling condition, take the mol ratio sorbyl alcohol: propylene oxide adds propylene oxide as the amount of 1: 3, and reaction is 2 hours under 60 ℃, and cooling rear discharging can obtain propylene oxide and the reaction product of sorbyl alcohol under the water existence;
(2) blend that step (1) is obtained with twin screw extruder extrude, pelletizing obtains pellet, the length-to-diameter ratio of twin screw extruder is 30: 1, diameter is 30mm, rotating speed 80rpm, it is as shown in table 1 that each distinguishes processing temperature:
Table 1
| Section | Charging zone | 2nd district | 3rd district | 4th district | 5th district | Head |
| Temperature/℃ | 170 | 200 | 220 | 220 | 220 | 220 |
In nitrogen atmosphere, be warming up to 240 ℃ from 0 ℃ of speed with 20 ℃/min, record the melting curve (DSC curve) of described pellet, as shown in Figure 2.Can find out from its DSC curve, the fusing point of PVA becomes two, and the melting peak area under high temperature reduces, and this explanation softening agent strengthens the melting point depression workability of PVA, is beneficial to its melt-processed.
(3) pellet that step (2) is obtained mixes in mixing tank with thermo-stabilizer and melt modification agent, 30 ℃ of mixing temperatures, and time 30min obtains uniform mixture, and airtight placement 72 hours under 50 ℃;
(4) mixture that step (3) is obtained is extruded with twin screw extruder and is obtained the composition melt, the twin screw length-to-diameter ratio is 40: 1, diameter 70mm, rotating speed 80rpm makes the said composition melt-flow flow directly into casting mold after the melt voltage-stabilizing system and obtains PVA (PVOH) FILM.The temperature of twin screw extruder sees Table 2:
Table 2
| Section | Charging zone | 2nd district | 3rd district | 4th district | 5th district | Head |
| Temperature/℃ | 80 | 100 | 140 | 150 | 150 | 150 |
(5) step (4) gained PVA (PVOH) FILM is removed moisture with the Infrared Heating method, temperature 50 C, and time 3min obtains PVA (PVOH) FILM.
Measure tensile strength and elongation at break according to GB GB/T 1040.3-2006, draw speed 20mm/min, the tensile strength of gained film is 21.09Mpa, elongation at break is 212.45%, the good mechanical performance of material.
Utilize WG7-S transmittance/mist degree determinator to measure.WG7-S transmittance/mist degree determinator is according to the GB2410-80 design, adopts microcomputer automatic operation display transparent rate and haze value simultaneously, and the mist degree of gained film is 8, and transparence is 90, illustrates that the light transmission of film is good.
Measuring the film water ratio with the film tester for water ratio is 8%.
Embodiment 3
The raw material that the present embodiment is used:
Preparation process:
(1) blend in mixing tank with polyvinyl alcohol powder and fluidizer, blending temperature is 60 ℃, time is 20min, wherein the preparation method of fluidizer sorbyl alcohol and propylene oxide reactant in water is: tetramethylolmethane and trolamine are added to the water with 10 % by weight and 5 % by weight of water respectively, under the reflux cooling condition, take mol ratio (tetramethylolmethane+trolamine): propylene oxide adds propylene oxide as the amount of 3: 1, reaction is 1.5 hours under 60 ℃, cooling rear discharging can obtain propylene oxide and sorbyl alcohol and the trolamine reaction product under water exists,
(2) blend that step (1) is obtained with twin screw extruder extrude, pelletizing obtains pellet, the length-to-diameter ratio of twin screw extruder is 30: 1, diameter is 30mm, rotating speed 80rpm, it is as shown in table 1 that each distinguishes processing temperature:
Table 1
| Section | Charging zone | 2nd district | 3rd district | 4th district | 5th district | Head |
| Temperature/ |
150 | 200 | 215 | 215 | 215 | 215 |
In nitrogen atmosphere, be warming up to 240 ℃ from 0 ℃ of speed with 20 ℃/min, record the melting curve (DSC curve) of described pellet, as shown in Figure 2.Can find out from its DSC curve, the fusing point of PVA becomes two, and the melting peak area under high temperature reduces, and this explanation softening agent strengthens the melting point depression workability of PVA, is beneficial to its melt-processed.
(3) pellet that step (2) is obtained mixes in mixing tank with thermo-stabilizer and melt modification agent, 30 ℃ of mixing temperatures, and time 30min obtains uniform mixture, and airtight placement 72 hours under 50 ℃;
(4) mixture that step (3) is obtained is extruded with twin screw extruder and is obtained the composition melt, the twin screw length-to-diameter ratio is 30: 1, diameter 45mm, rotating speed 50rpm makes the said composition melt-flow flow directly into casting mold after the melt voltage-stabilizing system and obtains PVA (PVOH) FILM.The temperature of twin screw extruder sees Table 2:
Table 2
| Section | Charging zone | 2nd district | 3rd district | 4th district | 5th district | Head |
| Temperature/℃ | 70 | 100 | 140 | 145 | 145 | 145 |
(5) step (4) gained PVA (PVOH) FILM is removed moisture with the Infrared Heating method, temperature 50 C, and time 3min obtains PVA (PVOH) FILM.
Measure tensile strength and elongation at break according to GB GB/T 1040.3-2006, draw speed 20mm/min, the tensile strength of gained film is 22.15Mpa, elongation at break is 192.45%, the good mechanical performance of material.
Utilize WG7-S transmittance/mist degree determinator to measure.WG7-S transmittance/mist degree determinator is according to the GB2410-80 design, adopts microcomputer automatic operation display transparent rate and haze value simultaneously, and the mist degree of gained film is 6, and transparence is 93, illustrates that the light transmission of film is good.
Measuring the film water ratio with the film tester for water ratio is 9%.
The raw material that the present embodiment is used:
Preparation process:
(1) blend in mixing tank with polyvinyl alcohol powder and fluidizer, blending temperature is 60 ℃, time is 20min, wherein the preparation method of fluidizer sorbyl alcohol and propylene oxide reactant in water is: tetramethylolmethane and trolamine are added to the water with 10 % by weight and 5 % by weight of water respectively, under the reflux cooling condition, take mol ratio (tetramethylolmethane+trolamine): propylene oxide adds propylene oxide as the amount of 3: 1, reaction is 1.5 hours under 60 ℃, cooling rear discharging can obtain propylene oxide and sorbyl alcohol and the trolamine reaction product under water exists,
(2) blend that step (1) is obtained with twin screw extruder extrude, pelletizing obtains pellet, the length-to-diameter ratio of twin screw extruder is 30: 1, diameter is 30mm, rotating speed 80rpm, it is as shown in table 1 that each distinguishes processing temperature:
Table 1
| Section | Charging zone | 2nd district | 3rd district | 4th district | 5th district | Head |
| Temperature/ |
150 | 200 | 215 | 215 | 215 | 215 |
In nitrogen atmosphere, be warming up to 240 ℃ from 0 ℃ of speed with 20 ℃/min, record the melting curve (DSC curve) of described pellet, as shown in Figure 2.Can find out from its DSC curve, the fusing point of PVA becomes two, and the melting peak area under high temperature reduces, and this explanation softening agent strengthens the melting point depression workability of PVA, is beneficial to its melt-processed.
(3) pellet that step (2) is obtained mixes in mixing tank with thermo-stabilizer and melt modification agent, 30 ℃ of mixing temperatures, and time 30min obtains uniform mixture.This mixture is extruded with twin screw extruder obtained the composition melt, the twin screw length-to-diameter ratio is 32: 1, diameter 50mm, and rotating speed 100rpm makes the said composition melt-flow flow directly into casting mold after the melt voltage-stabilizing system and obtains PVA (PVOH) FILM.The temperature of twin screw extruder sees Table 2:
Table 2
| Section | Charging zone | 2nd district | 3rd district | 4th district | 5th district | Head |
| Temperature/℃ | 70 | 100 | 140 | 145 | 145 | 145 |
(4) step (3) gained PVA (PVOH) FILM is removed moisture with the Infrared Heating method, temperature 50 C, and time 3min obtains PVA (PVOH) FILM.
Measure tensile strength and elongation at break according to GB GB/T 1040.3-2006, draw speed 20mm/min, the tensile strength of gained film is 20.05Mpa, elongation at break is 198.23%, the good mechanical performance of material.
Utilize WG7-S transmittance/mist degree determinator to measure.WG7-S transmittance/mist degree determinator is according to the GB2410-80 design, adopts microcomputer automatic operation display transparent rate and haze value simultaneously, and the mist degree of gained film is 6, and transparence is 93, illustrates that the light transmission of film is good.
Measuring the film water ratio with the film tester for water ratio is 10%.
Comparative Examples 1
Test according to the method for mentioning in CN200380103342.6.
The mixture of PVA resin material and G ﹠ W is mixed in super mixer, and described mixture is heated to 75 ℃ and be converted to low speed in advance, afterwards remix 5min.Until electric motor is compound when rising to maximum value and dropping to balance, add fumed silica, remix 1min removes mixture.
Above-mentioned composition is processed on twin screw extruder be blown into film, the extruding machine temperature is as shown in the table:
Table 3
| | Zone | 1 | |
Zone 3 | |
Die-head connecting sleeve | Head |
| Temperature/ |
100 | 175 | 190 | 195 | 195 | 195 |
Measure tensile strength and elongation at break according to GB GB/T 1040.3-2006, draw speed 20mm/min, tensile strength is 16.55Mpa, elongation at break is 189.32%.
The gained film has bubble, unfairness, and the transparence of film is 86, and mist degree is 4, and the transparency is relatively relatively poor.Measuring the film water ratio with the film tester for water ratio is 9.5%.
Claims (29)
1. the production method of a polyvinyl alcohol material, the method comprises the steps:
(1) blend in mixing tank with polyvinyl alcohol powder and softening agent;
(2) blend that step (1) is obtained with twin screw extruder extrude, pelletizing obtains pellet;
(3) pellet that step (2) is obtained mixes in mixing tank with thermo-stabilizer and melt modification agent, obtains uniform mixture, and airtight placement 24 ~ 96 hours;
(4) mixture that step (3) is obtained is extruded with twin screw extruder and is obtained the composition melt, makes the said composition melt-flow flow directly into the casting films tool after the voltage stabilizing of melt voltage-stabilizing system or sheet die obtains PVA (PVOH) FILM or sheet material;
Wherein, alternatively, above-mentioned steps (3), (4) are following step (3 '): the pellet that step (2) is obtained obtains the composition melt with directly extruding through twin screw extruder after thermo-stabilizer and melt modification agent mix in mixing tank, make the said composition melt-flow flow directly into the casting films tool after the voltage stabilizing of melt voltage-stabilizing system or sheet die obtains PVA (PVOH) FILM or sheet material
Wherein, polyvinyl alcohol powder 30 ~ 60 weight parts; Softening agent 10 ~ 60 weight parts; Thermo-stabilizer 0.1 ~ 5 weight part; Melt modification agent 0.1 ~ 3.5 weight part,
Wherein, described softening agent is in one or more and/or following material in water and following material two kinds or more than the mixture of two kinds of reaction product under water exists: C2 ~ C8 polyvalent alcohol, C3 ~ C15 ester, C3 ~ C15 ether, C3 ~ C15 amine and C3 ~ C15 epoxy compounds.
2. production method according to claim 1, wherein, polyvinyl alcohol powder 40 ~ 60 weight parts; Softening agent 20 ~ 50 weight parts; Thermo-stabilizer 0.2 ~ 3 weight part; Melt modification agent 0.2 ~ 2 weight part.
3. production method according to claim 1, wherein, in step (1), the temperature of blend is 30 ~ 150 ℃, the time of blend is 10 ~ 60min.
4. production method according to claim 3, wherein, in step (1), the temperature of blend is 50 ~ 130 ℃, the time of blend is 20 ~ 50min.
5. production method according to claim 1, wherein, the length-to-diameter ratio of the twin screw extruder in described step (2) is 28 ~ 48:1, and diameter is 30 ~ 65mm, and the condition of extruding comprises: temperature is 150 ~ 250 ℃, and rotating speed is 30-200rpm.
6. production method according to claim 5, wherein, the condition of extruding comprises: temperature is 170 ~ 240 ℃.
7. production method according to claim 5, wherein, the particle diameter of the pellet that is obtained by step (2) is 0.1 ~ 0.8mm.
8. production method according to claim 1, wherein, the temperature of mixing in step (3) and step (3 ') is 15 ~ 40 ℃, the time of mixing is 20 ~ 60min.
9. production method according to claim 1, wherein, in step (3), the temperature of airtight placement is 15 ~ 40 ℃.
10. production method according to claim 1, wherein, the length-to-diameter ratio of the twin screw extruder in described step (4) is 30 ~ 50:1, and diameter is 45 ~ 90mm, and the condition of extruding comprises: temperature is 40 ~ 200 ℃, and rotating speed is 50 ~ 150rpm; The length-to-diameter ratio of the twin screw extruder in described step (3 ') is 28 ~ 48:1, and diameter is 45 ~ 90mm, and the condition of extruding comprises: temperature is 150 ~ 250 ℃, and rotating speed is 50 ~ 150rpm.
11. production method according to claim 10, wherein, the extrusion condition of the twin screw extruder in described step (4) comprises: temperature is 50 ~ 180 ℃; The extrusion condition of the twin screw extruder in described step (3 ') comprises: temperature is 170 ~ 240 ℃.
12. production method according to claim 1, wherein, described step (4) and/or step (3 ') also are included in the process of extruding with twin screw extruder, extract the unreacted softening agent of part out with vacuum system.
13. production method according to claim 12, wherein, the amount of the softening agent of extraction is 10 ~ 30% of softening agent gross weight.
14. production method according to claim 12, wherein, the content of described composition melt polyvinyl alcohol when entering voltage-stabilizing system is 60 ~ 80% of composition total weight.
15. production method according to claim 1, wherein, when for the production of PVA (PVOH) FILM, this production method also is included in step (4) and/or step (3 ') is carried out Infrared Heating to the PVA (PVOH) FILM that obtains afterwards.
16. production method according to claim 15, wherein, Heating temperature is 20 ~ 60 ℃, and be 0.5 ~ 5min heat-up time.
17. according to claim 15 or 16 described production methods, wherein, carrying out Infrared Heating, to make the water ratio of described PVA (PVOH) FILM be 7 ~ 11 % by weight.
18. production method according to claim 1 and 2, wherein, the polymerization degree of described polyvinyl alcohol is 500 ~ 2000.
19. production method according to claim 18, wherein, the polymerization degree of described polyvinyl alcohol is 1700 ~ 2000.
20. production method according to claim 1 and 2, wherein, the alcoholysis degree of described polyvinyl alcohol is 88 ~ 99.9%.
21. production method according to claim 20, wherein, the alcoholysis degree of described polyvinyl alcohol is 98 ~ 99.9%.
22. production method according to claim 1, wherein, in described step (3) with the airtight placement of uniform mixture 24 ~ 72 hours.
23. production method according to claim 1 and 2, wherein, described softening agent is in one or more and/or following material in water and following material two kinds or more than the mixture of two kinds of reaction product under water exists: ethylene glycol, glycerol, tetramethylolmethane, neopentyl glycol, sorbyl alcohol, glycol ether, triglycol, molecular weight are 200 ~ 1000 polyoxyethylene glycol, TriMethylolPropane(TMP), diethanolamine, trolamine, triethylene tetramine, oxyethane, propylene oxide, 1-methyl propylene oxide, 1-butyl butylene oxide ring.
24. production method according to claim 1 and 2, wherein, described softening agent comprise propylene oxide and sorbyl alcohol under water exists reaction product or TriMethylolPropane(TMP) under water exists with the reaction product of diethanolamine and propylene oxide, its content is 5 ~ 50% of softening agent gross weight.
25. production method according to claim 1 and 2, wherein, described softening agent comprise propylene oxide and sorbyl alcohol under water exists reaction product or TriMethylolPropane(TMP) under water exists with the reaction product of diethanolamine and propylene oxide, its content is 10 ~ 30% of softening agent gross weight.
26. production method according to claim 1 and 2, wherein, in described softening agent, the content of water is the 20-90% of softening agent gross weight.
27. production method according to claim 22, wherein, described C2 ~ C8 polyvalent alcohol and C3 ~ C15 amine and reaction product thereof account for 10 ~ 30% of softening agent gross weight.
28. production method according to claim 1 and 2, wherein, described thermo-stabilizer is one or more in free radical absorption agent, free radical stabilizer, lubricant and active substance absorption agent.
29. production method according to claim 1 and 2, wherein, described melt modification agent is one or more in nano silicon, nano hydrotalcite, nano imvite and nanometer china clay.
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| TWI537287B (en) * | 2013-11-06 | 2016-06-11 | Chang Chun Petrochemical Co | Polyvinyl alcohol-based polymer film and method for producing the same |
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| CN111087726B (en) * | 2018-10-23 | 2023-06-06 | 中国石油化工股份有限公司 | High-viscosity polyvinyl alcohol composition, and preparation method and application thereof |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302606A (en) * | 1999-12-23 | 2001-07-11 | 强生消费者公司 | Method of preparing water soluble film |
| CN1711307A (en) * | 2002-11-15 | 2005-12-21 | 聚物股票上市公司 | Polyvinyl alcohol composition and film |
| CN1834146A (en) * | 2005-03-14 | 2006-09-20 | 东洋制铁化学株式会社 | Polyethylene resin combination and polyethylene film using same |
| EP1438175B1 (en) * | 2001-10-25 | 2007-03-07 | Multibase S.A.S. | Method for producing a thermoplastic composition based on polyvinyl alcohol free of unfused material and degradation |
| CN101565513A (en) * | 2008-11-26 | 2009-10-28 | 轻工业塑料加工应用研究所 | Heat stabilizer for producing PVA product and method for producing PVA product |
| CN102234405A (en) * | 2010-04-30 | 2011-11-09 | 常州百佳磁卡有限公司 | Water-resistant polyvinyl alcohol (PVA) film composition as well as fusion preparation method thereof |
| CN102286183A (en) * | 2011-06-17 | 2011-12-21 | 包头科瑞尔新材料有限公司 | Plastic polyvinyl alcohol (PVA) resin and preparation method thereof |
-
2011
- 2011-09-07 CN CN2011102642057A patent/CN102391598B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302606A (en) * | 1999-12-23 | 2001-07-11 | 强生消费者公司 | Method of preparing water soluble film |
| EP1438175B1 (en) * | 2001-10-25 | 2007-03-07 | Multibase S.A.S. | Method for producing a thermoplastic composition based on polyvinyl alcohol free of unfused material and degradation |
| CN1711307A (en) * | 2002-11-15 | 2005-12-21 | 聚物股票上市公司 | Polyvinyl alcohol composition and film |
| CN1834146A (en) * | 2005-03-14 | 2006-09-20 | 东洋制铁化学株式会社 | Polyethylene resin combination and polyethylene film using same |
| CN101565513A (en) * | 2008-11-26 | 2009-10-28 | 轻工业塑料加工应用研究所 | Heat stabilizer for producing PVA product and method for producing PVA product |
| CN102234405A (en) * | 2010-04-30 | 2011-11-09 | 常州百佳磁卡有限公司 | Water-resistant polyvinyl alcohol (PVA) film composition as well as fusion preparation method thereof |
| CN102286183A (en) * | 2011-06-17 | 2011-12-21 | 包头科瑞尔新材料有限公司 | Plastic polyvinyl alcohol (PVA) resin and preparation method thereof |
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