CN102304260A - Polyvinyl alcohol foaming material and manufacture method thereof - Google Patents
Polyvinyl alcohol foaming material and manufacture method thereof Download PDFInfo
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- CN102304260A CN102304260A CN201110201146A CN201110201146A CN102304260A CN 102304260 A CN102304260 A CN 102304260A CN 201110201146 A CN201110201146 A CN 201110201146A CN 201110201146 A CN201110201146 A CN 201110201146A CN 102304260 A CN102304260 A CN 102304260A
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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
- B29C48/36—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
- B29C48/397—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 a single screw
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Abstract
The invention provides a polyvinyl alcohol foaming material and a manufacture method thereof. The polyvinyl alcohol foaming material comprises the composition comprising the following components: 48-95 parts by weight of polyvinyl alcohol powder (preferably 67-95 parts by weight), 5-40 parts by weight of plasticizing agent (preferably 5-25 parts by weight), 0.05-5 parts by weight of nucleating agent (preferably 0.1-3 parts by weight), 0.1-2 parts by weight of heat stabilizer (preferably 0.2-0.8 part by weight), 0.02-5 parts by weight of cross linking agent (preferably 0.02-4 parts by weight) and the balance of chemical foaming agent or physical foaming agent. The manufacture method disclosed by the invention can be a chemical foaming method or a physical foaming method. The chemical foaming method has simple technology, does not have rigorous requirements on equipment and only needs a common single screw extruder used for foaming. The physical foaming method disclosed by the invention can use same foaming equipment, does not pollute environment and is a foaming method which is highly prized at present.
Description
Technical field
The present invention relates to a kind of polyvinyl alcohol foam material and method of manufacture thereof.
Background technology
Foamed polymer material was used widely in recent years, but foam material degradability in the market is poor, and environment is damaged, and it is necessary to substitute conventional polyolefins class foam material therefore to produce a kind of degradable foam material.
Z 150PH (PVA) is a kind of environment-friendly material, contains great amount of hydroxy group on the molecular chain, has hydrolyzable degraded and biodegradable characteristic, and is nonflammable, and products of combustion is water and carbonic acid gas, free from environmental pollution.Polyvinyl alcohol product has good organic solvent resistance, barrier and mechanical property.Therefore, replace common polyolefins foam material to be of great importance with Z 150PH for alleviation environmental pollution, minimizing white pollution.
Because the constructional feature of Z 150PH own causes melt temperature and decomposition temperature near being difficult to thermoplastic processing, its foaming product generally adopts solution foaming method or the preparation of moulded from foam method.Be that 201010533209.6 patent is carried out crosslinking curing with Z 150PH, frothing aid, linking agent, catalyzer like application number; Foaming in crosslinking curing link early stage or middle and later periods forms the porousness foam, and further cross-linking curing obtains the sponge matrix then.Publication number is in the patent of CN1289629, and the ultra-fine starch granules that adopts the process screening falls to obtain pore PVF sponge with starch wash as the abscess nucleator again behind Z 150PH colloidal sol curing molding.
The Z 150PH melt-processed has obtained solution in recent years, and the extrusion foaming technical costs is low, efficient is high, has received very big concern.Publication number is that the patent employing water of CN101153089 is whipping agent and softening agent, through swelling, melt-processed foaming.
Summary of the invention
The purpose of this invention is to provide that a kind of working method is simple, with low cost, physical strength is high, the preparation method of biodegradable polyvinyl alcohol foam material and simple possible.
Contriver of the present invention is through discover in a large number, only adds Z 150PH and nucleator and can not produce cell size distribution evenly and the PVA foam material of satisfactory mechanical property, and the melt strength of this and Z 150PH has direct relation.Under the low melt strength, because gaseous tension is excessive in the bubble, Z 150PH can not keep gas, and walls is prone to break; The abscess that generates is many to be existed with UNICOM, merging form, during high fondant-strength, because melt strength is excessive; The air bubble growth difficulty, but because bubble can not escape out, can only generate the bigger abscess of abscess-size in the PVA matrix; Perhaps owing to excessive merging of abscess that generates, cause expansion ratio not high, foaming effect is undesirable.Z 150PH can be controlled the melt strength of Z 150PH matrix with after fluidizer, nucleator, thermo-stabilizer and linking agent cooperate, and obtains being applicable to the foam material prescription of various foaming methods and whipping agent.
The invention provides a kind of polyvinyl alcohol foam material, it is made by the compsn that comprises following component: Z 150PH powder 48～95 weight parts, preferred 67～95 weight parts; Fluidizer 5～40 weight parts, preferred 5～25 weight parts; Nucleator 0.05～5 weight part, preferred 0.1～3 weight part; Thermo-stabilizer 0.1～2 weight part, preferred 0.2～0.8 weight part; Linking agent 0.02～5 weight part, preferred 0.02～4 weight part; And chemical foaming agent or pneumatogen.
According to polyvinyl alcohol foam material provided by the invention, wherein, the polymerization degree of said Z 150PH can be 500～2500, preferred 1700～2000.The alcoholysis degree of the Z 150PH among the present invention can be 74～99%; Concrete alcoholysis degree end properties is as required confirmed: for needing the water-soluble sample of low temperature; Preferred alcoholysis degree is 74～88%; Not water-soluble for low temperature, need the sample of the water-soluble and good barrier property of high temperature, preferred alcoholysis degree is 89～99%.In addition, two or more Z 150PH that can mix are to obtain appropriate performance.The viscosity of the high more melt of molecular weight is big more, degraded more easily during high temperature, and melt-processed is more difficult.Therefore the present invention adopts different amounts and different types of thermo-stabilizer and secondary process auxiliary agent according to different Z 150PH molecular weight and alcoholysis degree.For example; Alcoholysis degree can discharge acetic gas when being 88% pva degradation, therefore wants the auxiliary acid absorption agent, and the Z 150PH of high alcoholysis degree is very big owing to Intermolecular Forces; The degraded that causes is serious; Therefore need to add lubricant to increase the flowability of high alcoholysis degree Z 150PH, reduce its degraded, specific embodiments will embody in an embodiment.
Z 150PH powder as raw material of the present invention can be the various PVA raw materials that are purchased; For example can be PVA series product, Gohsenol (from Nippon Gonhsei), Poval (from Kuraray), Celvol (from Celanese) and the CCP (from the Changchun petroleum chemistry) of Japanese Kuraray; Be preferably the PVA117 (alcoholysis degree 99% of Japanese Kuraray; The polymerization degree 1700), PVA217 (alcoholysis degree 88%, the polymerization degree 1700) and PVA2088 (alcoholysis degree 88%, the polymerization degree 2000).
According to polyvinyl alcohol foam material provided by the invention; Wherein, Said fluidizer be following one or more; Be included as terepthaloyl moietie, polyoxyethylene glycol, USP Kosher, tetramethylolmethane, hexanolactam, Ucar 35, TriMethylolPropane(TMP), pentanediol, sorbyl alcohol, thanomin, diethylolamine, one or more in ethanamide, N and the quadrol are preferably in terepthaloyl moietie, USP Kosher, tetramethylolmethane, hexanolactam and the diethylolamine one or more.
Table 1 has been listed the plasticizing data of high alcoholysis degree PVA117, wherein.Can find out that from table 1 behind the adding fluidizer, the fusing point of plasticizing PVA all decreases with respect to pure PVA, the fusing point that has significantly reduced PVA after the composite fluidizer of the present invention adds is described, make 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 percent crystallinity (X
c) also purer PVA decreases; The adding that fluidizer is described has weakened the intermolecular and intramolecular hydrogen bond action of PVA; And new hydrogen bond generates and causes the PVA regularity to descend between fluidizer and the PVA, because fluidizer gets in the PVA molecular chain, fluidizer need move out of the PVA molecular chain and could accomplish crystallization when crystallization; Crystallization behavior is postponed, and percent crystallinity reduces.Fluidizer of the present invention can be realized the melt-processed of high alcoholysis degree PVA.
Table 1
Said nucleator can be inorganic nucleator such as talcum powder, lime carbonate, nano imvite, nanoclay, Nano carbon white, mica; Preferably; The particle diameter of said inorganic nucleator can be 200～3000 orders; Preferred 1000-3000 order, water ratio≤0.5% also can be organic nucleating agent; Like carboxylic acid and metallic salt thereof, glucitols, aryl phosphoric acids salt, RA rosin acid class, perhaps the polyoxyethylene glycol of polymer nucleator such as molecular weight 400～1000, HEC (PVA0588) in one or more.Can confirm the particle diameter and the consumption of nucleator according to different abscess needs.
Said thermo-stabilizer can be the conventional thermo-stabilizer in this area.For example, can be in radical absorption agent, free radical stabilizer, lubricant and the active substance absorption agent one or more.In a kind of embodiment preferred; Said radical absorption agent can comprise main absorption agent and help absorption agent, main absorption agent can comprise alkylphenol compounds, alkylidene group phenolic cpd, alkyl bisphenol compound, hydroxy phenyl acrylic ester compound, aminophenols, thiobisphenol compounds or its combination.Help absorption agent to comprise ester OH 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 said free radical stabilizer can comprise organic salt that metals such as Ca, Ba, Sn form, formed by Zn or Cd etc.Said lubricant can comprise hydro carbons lubricant such as solid paraffin, whiteruss; Fatty acid such as Triple Pressed Stearic Acid, ricinolic acid; Aliphatic amide type and ester class; Like stearylamide, butyl stearate, stearin, and the metallic soap class, like in Zinic stearas, barium stearate, the calcium stearate one or more.Said 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 the preferable case; The thermo-stabilizer that the present invention uses can be alkylphenol compounds, alkylidene group phenolic cpd, alkyl bisphenol compound, hydroxy phenyl acrylic ester compound, aminophenols, thiobisphenol compounds, ester OH compounds, saturated acid ester compound, 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; In the 3-cyclohexadione compounds one or more are preferably in alkylphenol compounds, thiobisphenol compounds, monothioester compounds, inferior phosphide compounds, barium stearate and the calcium stearate one or more.Particularly, it is the thermo-stabilizer described in 200810180879.7 the patented claim that the thermo-stabilizer that the present invention uses can be preferably application number, and it is introduced this paper as a reference in full.
Said linking agent can be the organosilane class, like vinyl silanes, epoxy radicals silicone hydride, aminosilane class, and too esters of gallic acid such as monoalkyl type titanic acid ester, monoalkoxy phosphate type titanic acid ester, organic chromium class, titanium class (TiO
2) and silicon class, like in nano silicon, organic dibasic acid and the polyvalent alcohol one or more, be preferably nano silicon or polyvalent alcohol.
Said chemical foaming agent can be any chemical foaming agent well known in the art; For example; Can for azodicarbonamide foaming agent, sodium hydrogencarbonate, Diisopropyl azodicarboxylate, hydrazides, methyne tetramine with in one or more, be preferably azodicarbonamide foaming agent or sodium hydrogencarbonate.The consumption of said chemical foaming agent can be confirmed according to needed foaming degree by those skilled in the art at an easy rate; Generally speaking; Z 150PH with 100 weight parts is a benchmark, and the consumption of chemical foaming agent can be 0.08～5 weight part, preferred 0.2～2 weight part.Said pneumatogen can be any pneumatogen well known in the art, for example, can be supercritical gas, is preferably in overcritical nitrogen, supercritical co and the overcritical butane one or more, is preferably overcritical nitrogen.Z 150PH with 100kg is a benchmark, and the consumption of supercritical gas can be 0.5～5 liter, is preferably 1～3 liter.
The present invention also provides the method A that makes above-mentioned polyvinyl alcohol foam material (chemical blowing process), and this method comprises the steps:
(1) with Z 150PH powder and fluidizer blend in mixing tank;
(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 processing aid, obtains even mixed materials;
(4) in the mixture that step (3) obtains, add chemical foaming agent, mix back extruding and obtain the polyvinyl alcohol foam goods with single screw extrusion machine or many placed in-line single screw extrusion machines;
Wherein, alternatively, above-mentioned steps (2), (3) are following step (2 '): the mixture that step (1) is obtained mixes in mixing tank with processing aid and chemical foaming agent, obtains even mixed materials; And above-mentioned steps (4) is a following step (3 '): the mixture that step (2 ') is obtained is extruded with single screw extrusion machine or many placed in-line single screw extrusion machines and is obtained the polyvinyl alcohol foam goods.
In aforesaid method A (that is, chemical blowing process), the method for carrying out according to step (1) (2) (3) (4) can be called chemical foaming agent dual-step type foaming; The method of carrying out according to step (1) (2 ') (3 ') can be called chemical foaming agent and extrude the single step foaming continuously.
The present invention also provides the another kind of method B that makes above-mentioned polyvinyl alcohol foam material (physical blowing method), and this method comprises the steps:
(a) with Z 150PH powder and fluidizer blend in mixing tank;
(b) blend that step (a) is obtained with twin screw extruder extrude, pelletizing obtains pellet;
(c) pellet that step (b) is obtained mixes in mixing tank with processing aid (nucleator, linking agent, thermo-stabilizer), obtains even mixed materials;
(d) mixture that step (c) is obtained is extruded with single screw extrusion machine or many placed in-line single screw extrusion machines, in extrusion, supercritical gas is injected the Z 150PH melt, obtains the polyvinyl alcohol foam goods;
Wherein, alternatively, above-mentioned steps (b), (c) are following step (b '): the blend that step (a) is obtained mixes in mixing tank with processing aid (nucleator, linking agent, thermo-stabilizer), obtains even mixed materials; And above-mentioned steps (d) is following step (c '): the mixture that step (b ') obtains is extruded with single screw extrusion machine or many placed in-line single screw extrusion machines; In extrusion, supercritical gas is injected the Z 150PH melt, obtain the polyvinyl alcohol foam goods.
In aforesaid method B (that is, the physical blowing method), according to step (a) (b) (c) method of (d) carrying out can be called pneumatogen dual-step type foaming; The method of carrying out according to step (a) (b ') (c ') can be called pneumatogen and extrude the single step foaming continuously.
According to method of manufacture provided by the invention, wherein, in step (1) with (a), 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.
Said step (2) and (b) in twin screw extruder can be preferably length-to-diameter ratio 28～32: 1, the twin screw extruder of diameter 30～65mm; Be preferably parallel parallel dual-screw extruding machine; The condition of extruding comprises: temperature can be 150～250 ℃, preferred 170～240 ℃; Rotating speed can be 30～200 revolutions per seconds, preferred 50～150 revolutions per seconds.Under the preferable case, be 0.1～0.8mm by the particle diameter of step (2) and the pellet that (b) obtains.For example, a kind of preferred embodiment in, under slight shock conditions, 20 kilograms of pellets in 5min gross weight about 95% can pass through 25 purpose screen clothes, about 99% of gross weight can be passed through 20 purpose screen clothes.
According to method of manufacture provided by the invention, wherein, step (3) and (c) in the blended temperature can be 20～40 ℃, the blended time can be 5～30min.
Manufacturing method according to the invention, wherein, method A and B are respectively the embodiment that adopts chemical blowing process and physical blowing method.Wherein, the length-to-diameter ratio of the single screw extrusion machine among said step (4), (d), (3 ') and (c ') can be 28～60: 1, and diameter can be 30～65mm, and the condition of extruding comprises: temperature can be 150～250 ℃, preferred 170～240 ℃; Rotating speed can be 5～150 revolutions per seconds, preferred 10～100 revolutions per seconds.
Manufacturing method according to the invention, in step (2 ') and (b '), the blended temperature can be 5～80 ℃, is preferably 20～60 ℃, the time of blend can be 10～50min, is preferably 20～40min.
In chemical blowing process; Said chemical foaming agent can be any chemical foaming agent well known in the art; For example; Can for azodicarbonamide foaming agent, sodium hydrogencarbonate, Diisopropyl azodicarboxylate, hydrazides, methyne tetramine with in one or more, be preferably azodicarbonamide foaming agent or sodium hydrogencarbonate.The consumption of said chemical foaming agent can be confirmed according to needed foaming degree by those skilled in the art at an easy rate; Generally speaking; Z 150PH with 100 weight parts is a benchmark, and the consumption of chemical foaming agent can be 0.08～5 weight part, preferred 0.2～2 weight part.In the physical blowing method, employed pneumatogen is a supercritical gas, can be in overcritical nitrogen, supercritical co and the overcritical butane one or more, is preferably overcritical nitrogen.
Chemical blowing process technology of the present invention is simple, and is not harsh to equipment requirements, only needs the common single screw extrusion machine that is used to foam to get final product; Physical blowing method of the present invention also can be used same foaming machine, and non-environmental-pollution is current foaming method of praising highly energetically.
The key distinction of the present invention and prior art (like the patent of publication number CN101153089) is; The whipping agent that the present invention adopts is not a water; And make polyvinyl alcohol pellet after can earlier Z 150PH being plastified through fluidizer in the foaming process; Then polyvinyl alcohol pellet and whipping agent, processing aid etc. are carried out continuous extrusion foaming on single screw extrusion machine and also can fluidizer and whipping agent, processing aid etc. be mixed together in the twin screw extruder extrusion foaming continuously, perhaps adopt the method foaming of supercritical gas foaming.The polyvinyl alcohol foam material that makes can be used for water treatment with filtration and sorbing material, sound insulation and lagging material, soil moisturizing, fresh-keeping and multi-functional composite foam material.
Description of drawings
Below, specify embodiment of the present invention in conjunction with accompanying drawing, wherein:
The sem photograph of the polyvinyl alcohol foam material that Fig. 1 makes for the embodiment of the invention 1;
The sem photograph of the polyvinyl alcohol foam material that Fig. 2 makes for the embodiment of the invention 2;
The sem photograph of the polyvinyl alcohol foam material that Fig. 3 makes for the embodiment of the invention 3;
Fig. 4 A-B is the schematic flow sheet of chemical blowing process of the present invention, and wherein Fig. 4 A is a chemical foaming agent dual-step type foaming; Fig. 4 B is that chemical foaming agent is extruded the single step foaming continuously;
Fig. 5 A-B is the schematic flow sheet of physical blowing method of the present invention, and wherein Fig. 5 A is a pneumatogen dual-step type foaming; Fig. 5 B is that pneumatogen is extruded the single step foaming continuously;
The sem photograph of the polyvinyl alcohol foam material that Fig. 6 makes for Comparative Examples 1;
The sem photograph of the polyvinyl alcohol foam material that Fig. 7 makes for Comparative Examples 2;
The sem photograph of the polyvinyl alcohol foam material that Fig. 8 makes for Comparative Examples 3.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, the embodiment that provides has been merely and has illustrated the present invention, rather than in order to limit scope of the present invention.
Present embodiment prepares foam material according to method of manufacture of the present invention with chemical blowing process
Present embodiment is raw materials used:
Z 150PH powder (Japanese Kuraray, PVA217) 100kg;
Hexanolactam (fluidizer) 10kg;
Terepthaloyl moietie (fluidizer) 15kg
Talcum powder (nucleator) 0.5kg;
Silicon-dioxide (linking agent) 3kg;
Tin octylate T890 (thermo-stabilizer, Guangzhou are stepped on magnificent chemical industry ltd) 0.5kg;
DSTP (phosphite ester kind antioxidant, Beijing Assistants Inst.) 0.2Kg
Cellmic C 121 (chemical foaming agent, the safe chemical industry of Henan Province's gold) 0.5kg;
Marinco H (acid absorber) 0.2kg.
With above-mentioned feedstock production foam material:
(1) in high-speed mixer with Z 150PH powder and hexanolactam, terepthaloyl moietie, oxidation inhibitor 1098 and DSTP blend; Remain temperature in the mixing process below 100 ℃; Mixing time is powdery during the mixture discharging with till above-mentioned mixture is mixed;
(2) blend that step (1) is obtained uses that twin screw extruder is extruded, pelletizing obtains the pellet of particle diameter as 0.5mm, and wherein, the length-to-diameter ratio of this twin screw extruder is 30: 1, and diameter is 50mm, rotating speed 50rpm, and it is as shown in table 2 that each distinguishes temperature:
Table 2
| Section | Charging zone | 2 districts | 3 districts | 4 districts | 5 districts | Head |
| Temperature/℃ | 160 | 180 | 210 | 210 | 190 | 185 |
(3) pellet that in high-speed mixer, step (2) is made mixes with linking agent, nucleator, whipping agent, and temperature remains at below 30 ℃ in the mixing process, and the about 5min of mixing time obtains mixture;
(4) mixture that step (3) is obtained is extruded through single screw extrusion machine and is obtained polyvinyl alcohol foam material, and wherein, the length-to-diameter ratio of this single screw extrusion machine is 40: 1, and diameter is 30mm, rotating speed 30rpm, and it is as shown in table 3 that each distinguishes temperature:
Table 3
| Section | Charging zone | 2 districts | 3 districts | 4 districts | 5 districts | Head |
| Temperature/℃ | 165 | 190 | 220 | 220 | 190 | 180 |
According to GB GB/T6343-1995, (ULTRAPYC 1200e, Quantachrome Instruments) carries out density measurement through density tester, measures tensile strength and elongation at break according to GB GB/T 6344-1996.The sem photograph of the foam material that present embodiment makes is as shown in Figure 1, as can beappreciated from fig. 1, gained PVA foam material, distribution of cells is even, and wall thickness is even, does not have abscess to merge phenomenon, and abscess-size is approximately 250um.The prepared foam material tensile strength of the present invention is 13.6MPa, and elongation at break is 183.8%, and apparent density is 0.42g/cc.
Embodiment 2
Present embodiment is equipped with foam material according to method of manufacture of the present invention with the physical blowing legal system
Present embodiment is raw materials used:
Z 150PH powder (Japanese Kuraray, PVA117) 100kg;
Tetramethylolmethane (fluidizer) 15kg;
TriMethylolPropane(TMP) (fluidizer) 8kg;
Lime carbonate (nucleator, Qingdao rich letter chemical industry ltd 2000 orders) 0.15kg;
Nanoclay (nucleator) 0.22kg;
Calcium stearate (lubricant) 0.3kg;
Hinered phenols antioxidant 1076 (Beijing Assistants Inst.) 0.10kg
Phosphorous acid ester thermo-stabilizer (Beijing Assistants Inst.) 0.3kg;
(1) in high-speed mixer with Z 150PH powder and tetramethylolmethane, thermo-stabilizer and TriMethylolPropane(TMP) blend, the temperature of blend remains on below 49 ℃, the time of blend is 50min, is Powdered during the mixture discharging;
(2) blend that step (1) is obtained uses that twin screw extruder is extruded, pelletizing obtains the pellet of particle diameter as 0.8mm, and wherein, the length-to-diameter ratio of this twin screw extruder is 32: 1, and diameter is 40mm, rotating speed 140rpm, and it is as shown in table 4 that each distinguishes temperature:
Table 4
| Section | Charging zone | 2 districts | 3 districts | 4 districts | 5 districts | Head |
| Temperature/℃ | 160 | 180 | 210 | 210 | 210 | 208 |
(3) pellet that in high-speed mixer, step (2) is made mixes with linking agent, nucleator, and temperature is 25 ℃ in the mixing process, mixes about 10min, obtains mixture;
(4) mixture that step (3) is obtained is extruded through single screw extrusion machine, through the supercritical gas injected system with overcritical N
2Inject Z 150PH melt (system pressure is 12MPa, and IR is 2 liters) in the 2nd district, make overcritical N
2In screw rod, exist, mix, make liquid and Z 150PH melt thorough mixing even through screw rod shearing with liquid form; Through port mould, pressure release, extrude, cooling forming, obtain polyvinyl alcohol foam material, wherein; The length-to-diameter ratio of this single screw extrusion machine is 55: 1; Diameter is 60mm, and rotating speed adopts 10,15,20,30,40 and 80rpm respectively, and it is as shown in table 5 that each distinguishes temperature:
Table 5
| Section | Charging zone | 2 districts | 3 districts | 4 districts | 5 districts | Head |
| Temperature/℃ | 180 | 230 | 230 | 225 | 220 | 205 |
The sem photograph of the foam material that under different rotating speeds, makes in the present embodiment is as shown in Figure 2; Wherein a, b, c, d, e and f are followed successively by and adopt 10,15,20,30,40 and the Electronic Speculum figure of the foam material that obtains of 80rpm rotating speed; Contrast a, b, c, d, e and f can find out; Under low shear rate, cell density is big and distribution of cells is even, along with the raising distribution of cells and the size of screw speed are inhomogeneous.Along with the raising of rotating speed, the PVA melt viscosity descends, and the abscess that has therefore occurred among the figure b merges phenomenon; Bubble is rendered as the circular or oval of distortion, and some abscesses do not possess complete bubble wall, has more cavity; Percentage of open area improves, and the expansion ratio of foam material descends, and bubble density rises; Apparent density and screw speed relation are as shown in table 6, and the Mechanical test results of foam material shows that the mechanical property of foam material and the cell density of material have much relations; Tensile strength of material that distribution of cells is even and cell morphology is complete and elongation at break are all higher; If the material abscess merges serious, or distribution of cells is inhomogeneous, then the mechanical property of material is relatively poor.
Table 6
| Screw speed (rpm) | 10 | 15 | 20 | 30 | 40 | 80 |
| Density (g/cc) | 0.46 | 0.54 | 0.59 | 0.67 | 0.83 | 0.87 |
Embodiment 3
Present embodiment prepares foam material according to method of manufacture of the present invention with chemical blowing process
Present embodiment is raw materials used:
Z 150PH powder (Japanese Kuraray, PVA2088) 100kg;
USP Kosher (fluidizer) 5kg;
Pentanediol (fluidizer) 5kg
PEG 400 (nucleator, Chemical Reagent Co., Ltd., Sinopharm Group) 0.5kg;
Mica (nucleator) 0.22kg;
Zinic stearas (lubricant) 0.3kg;
AO31 (Beijing Assistants Inst.) 0.1Kg;
AO-5 (Beijing Assistants Inst.) 0.2Kg;
Phosphorous acid ester thermo-stabilizer (Beijing Assistants Inst.) 0.4kg;
Sodium hydrogencarbonate (acid absorber) 2kg;
Diisopropyl azodicarboxylate (chemical foaming agent) 0.3kg.
(1) in high-speed mixer with Z 150PH powder and USP Kosher, pentanediol, thermo-stabilizer, linking agent, nucleator and chemical foaming agent sodium hydrogencarbonate, Diisopropyl azodicarboxylate blend, the temperature of blend is 49 ℃, the time of blend is 50min;
(2) blend that step (1) is obtained is with the direct extrusion foaming of twin screw extruder, and wherein, the length-to-diameter ratio of this twin screw extruder is 32: 1, and diameter is 40mm, rotating speed 140rpm, and it is as shown in table 7 that each distinguishes temperature:
Table 7
| Section | Charging zone | 2 districts | 3 districts | 4 districts | 5 districts | Head |
| Temperature/℃ | 160 | 180 | 200 | 220 | 220 | 220 |
Fig. 3 is the SEM picture of embodiment foam material, and as can be seen from the figure, abscess-size is about 200um, and abscess is even, and the big gun hole wall is thinner.
According to measuring with embodiment 1 identical method, the tensile strength of the foam material that present embodiment makes reaches 15.6Mpa, and elongation at break is 163.8%, and apparent density is 0.35g/cc, and expansion ratio is 3.8 times.
Comparative Examples 1
Method of manufacture according among the CN101153089 prepares foam material
It is even that 2kg T 46155 and 2kg LUTARALDEHYDE are joined the 15kg deionized water for stirring; The polyvinyl alcohol pellet 45kg that adds the polymerization degree 1700, alcoholysis degree 92mol.%; Under stirring action in the encloses container of 60 ℃ of temperature abundant swelling, after abundant swelling, add 2kg lime carbonate, 20kg Walocel MT 20.000PV again; After mixing, in the forcing machine of 170 ℃ of temperature, melt extrude foaming preparation polyvinyl alcohol foam sheet material.
Fig. 6 is the SEM picture of this Comparative Examples foam material, and as can be seen from the figure, the foam material abscess-size is inhomogeneous, and it is serious that abscess merges phenomenon, and cell wall is very thick, and foam process is wayward.
Comparative Examples 2
Method of manufacture according among the CN101153089 prepares foam material
It is even that 0.5kg Hydrocerol A, 0.5kg borax and 5kg urea are joined the 40kg deionized water for stirring; The polyvinyl alcohol pellet 50kg that adds the polymerization degree 900, alcoholysis degree 99mol.%; Under stirring action in the encloses container of 40 ℃ of temperature abundant swelling, after abundant swelling, add 5kg silicon-dioxide, 4kg oleic acid acyl ammonium and 15kg gac again; After mixing, preparation polyvinyl alcohol foam bead in the thermocompressor of 140 ℃ of temperature.
Fig. 7 is the SEM picture of this Comparative Examples foam material, as can be seen from the figure, the cell size distribution broad, abscess-size is big, and abscess merging phenomenon is serious.
Comparative Examples 3
Method of manufacture according among the CN101153089 prepares foam material
It is even that 1kg epoxy chloropropane, 4kg polyoxyethylene glycol and 6kg ethanamide are joined the 15kg deionized water for stirring; The polyvinyl alcohol pellet 85kg that adds the polymerization degree 2400, alcoholysis degree 92mol.%; Under stirring action in the encloses container of 50 ℃ of temperature abundant swelling, after abundant swelling, add 2kg talcum powder, 2kg Zinic stearas and 10kg chitosan again; After mixing, preparation polyvinyl alcohol foam film in the thermocompressor of 150 ℃ of temperature.
Fig. 8 is the SEM picture of this Comparative Examples foam material, and as can be seen from the figure, PVA foam material distribution of cells is uneven, and some local bubble is intensive, and some is sparse, even does not have bubble, abscess that the merging phenomenon is arranged, and the material expansion ratio is little.
Measure tensile strength, elongation at break, apparent density and the expansion ratio of the foam material that Comparative Examples 1-3 makes according to the method identical with embodiment 1, the result lists in table 8.
Table 8
| Sample | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 |
| Tensile strength (MPa) | 12.50 | 13.13 | 9.64 |
| Elongation at break (%) | 156.71 | 176.70 | 147.67 |
| Apparent density (g/cc) | 1.29 | 1.26 | 1.19 |
| Expansion ratio | 1.03 | 1.05 | 1.12 |
The data of data in the table 8 and embodiment of the invention sample are compared and can find out, the mechanical property of comparative example is not as good as the inventive method PVA foaming product, and expansion ratio is also less.
Claims (15)
1. polyvinyl alcohol foam material, it is made by the compsn that comprises following component: Z 150PH powder 48～95 weight parts, preferred 67～95 weight parts; Fluidizer 5～40 weight parts, preferred 5-25 weight part; Nucleator 0.05～5 weight part, preferred 0.1～3 weight part; Thermo-stabilizer 0.1～2 weight part, preferred 0.2～0.8 weight part; Linking agent 0.02-5 weight part, preferred 0.02-4 weight part; And chemical foaming agent or pneumatogen.
2. polyvinyl alcohol foam material according to claim 1, wherein, the polymerization degree of said Z 150PH can be 500～2500, preferred 1700～2000; Preferably, the alcoholysis degree of said Z 150PH is 74～99%.
3. polyvinyl alcohol foam material according to claim 1 and 2; Wherein, Said fluidizer is terepthaloyl moietie, polyoxyethylene glycol, USP Kosher, tetramethylolmethane, hexanolactam, Ucar 35, TriMethylolPropane(TMP), pentanediol, sorbyl alcohol, thanomin, diethylolamine; In ethanamide, N and the quadrol one or more are preferably in terepthaloyl moietie, USP Kosher, tetramethylolmethane, hexanolactam and the diethylolamine one or more.
4. according to each described polyvinyl alcohol foam material in the claim 1 to 3; Wherein, Said nucleator is one or more in inorganic nucleator or the organic nucleating agent, and said inorganic nucleator is talcum powder, lime carbonate, nano imvite, nanoclay, Nano carbon white and mica, preferably; The particle diameter of said inorganic nucleator is 200～3000 orders, water ratio≤0.5%; Said organic nucleating agent is carboxylic acid and metal-salt, glucitols, aryl orthophosphate, RA rosin acid class or polymer nucleator, one or more among the PVA of said polymer nucleator such as polyoxyethylene glycol, low polymerization degree.
5. according to each described polyvinyl alcohol foam material in the claim 1 to 4, wherein, said thermo-stabilizer is one or more in radical absorption agent, free radical stabilizer, lubricant and the active substance absorption agent.
6. according to each described polyvinyl alcohol foam material in the claim 1 to 5; Wherein, Said linking agent is the organosilicon alkanes; Like vinyl silanes, epoxy radicals silicone hydride, aminosilane class, titanate ester,, be preferably nano silicon or polyvalent alcohol like in monoalkyl type titanic acid ester and monoalkoxy phosphate type titanic acid ester, organic chromium class, titanium class and silicon class, organic dibasic acid and the polyvalent alcohol one or more.
7. according to each described polyvinyl alcohol foam material in the claim 1 to 6; Wherein, Said chemical foaming agent be azodicarbonamide foaming agent, sodium hydrogencarbonate, Diisopropyl azodicarboxylate, hydrazides, methyne tetramine with in one or more, be preferably azodicarbonamide foaming agent or sodium hydrogencarbonate; Preferably, be benchmark with the Z 150PH of 100 weight parts, the consumption of said chemical foaming agent is 0.08～5 weight part, more preferably 0.2～2 weight part; Said pneumatogen is a supercritical gas, is preferably in overcritical nitrogen, supercritical co and the overcritical butane one or more, most preferably is overcritical nitrogen; Preferably, be benchmark with the Z 150PH of 100kg, the consumption of said supercritical gas is 0.5～5 liter, more preferably 1～3 liter.
8. method of making each described polyvinyl alcohol foam material in the claim 1 to 7, this method comprises the steps:
(1) with Z 150PH powder and fluidizer blend in mixing tank;
(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 nucleator, thermo-stabilizer and linking agent, obtains even mixed materials;
(4) in the mixture that step (3) obtains, add chemical foaming agent, mix back extruding and obtain the polyvinyl alcohol foam goods with single screw extrusion machine or many placed in-line single screw extrusion machines;
Wherein, alternatively, above-mentioned steps (2), (3) are following step (2 '): the mixture that step (1) is obtained mixes in mixing tank with nucleator, thermo-stabilizer, linking agent and chemical foaming agent, obtains even mixed materials; And above-mentioned steps (4) is a following step (3 '): the mixture that step (2 ') is obtained is extruded with single screw extrusion machine or many placed in-line single screw extrusion machines and is obtained the polyvinyl alcohol foam goods.
9. method of making each described polyvinyl alcohol foam material in the claim 1 to 7, this method comprises the steps:
(a) with Z 150PH powder and fluidizer blend in mixing tank;
(b) blend that step (a) is obtained with twin screw extruder extrude, pelletizing obtains pellet;
(c) pellet that step (b) is obtained mixes in mixing tank with nucleator, thermo-stabilizer and linking agent, obtains even mixed materials;
(d) mixture that step (c) is obtained is extruded with single screw extrusion machine or many placed in-line single screw extrusion machines, in extrusion, supercritical gas is injected the Z 150PH melt, obtains the polyvinyl alcohol foam goods;
Wherein, alternatively, above-mentioned steps (b), (c) are following step (b '): the blend that step (a) is obtained mixes in mixing tank with nucleator, thermo-stabilizer and linking agent, obtains even mixed materials; And above-mentioned steps (d) is following step (c '): the mixture that step (b ') obtains is extruded with single screw extrusion machine or many placed in-line single screw extrusion machines; In extrusion, supercritical gas is injected the Z 150PH melt, obtain the polyvinyl alcohol foam goods.
10. according to Claim 8 or 9 described methods, wherein, in step (1) with (a), the temperature of blend is 30～150 ℃, is preferably 50～130 ℃, and the time of blend is 10～60min, is preferably 20～50min.
11. according to Claim 8 or 9 described methods, wherein, said step (2) and (b) in the length-to-diameter ratio of twin screw extruder be 28～32: 1, diameter is 30～65mm, the condition of extruding comprises: temperature is 150～250 ℃, preferred 170～240 ℃; Rotating speed is 30-200 revolutions per second.
12. according to Claim 8 or 9 described methods, wherein, be 0.1～0.8mm by the particle diameter of step (2) and the pellet that (b) obtains.
13. according to Claim 8 or 9 described methods, wherein, step (3) and (c) in the blended temperature be 20-40 ℃, the blended time is 5～30min.
14. according to Claim 8 or 9 described methods; Wherein, the length-to-diameter ratio of single screw extrusion machine is 28～60: 1 described in step (4), (d), (3 ') and (c '), and diameter is 30～65mm; The condition of extruding comprises: temperature is 150～250 ℃, preferred 170～240 ℃; Rotating speed is 5-150 revolutions per second.
15. according to Claim 8 or 9 described methods, wherein, the blended temperature is 5～80 ℃ among step (2 ') and (b '), is preferably 20～60 ℃, and the blended time is 10～50min, is preferably 20～40min.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153089A (en) * | 2007-09-06 | 2008-04-02 | 四川大学 | Polyvinyl alcohol polarity sponge plastics and method of producing the 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 |
-
2011
- 2011-07-18 CN CN201110201146A patent/CN102304260A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153089A (en) * | 2007-09-06 | 2008-04-02 | 四川大学 | Polyvinyl alcohol polarity sponge plastics and method of producing the 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 |
Non-Patent Citations (2)
| Title |
|---|
| 康智勇 等: "环境友好聚乙烯醇粘合剂研究", 《中国胶粘剂》, vol. 14, no. 3, 31 March 2005 (2005-03-31) * |
| 王茹 等: "改性聚乙烯醇的热性能", 《塑料工业》, vol. 30, no. 1, 31 January 2002 (2002-01-31) * |
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