CN102286183B - Plastic polyvinyl alcohol (PVA) resin and preparation method thereof - Google Patents
Plastic polyvinyl alcohol (PVA) resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses plastic polyvinyl alcohol (PVA) resin and a preparation method thereof, and belongs to the field of plastic resin. The plastic PVA resin solves the technical problem that continuous production is affected by poor stability of PVA resin. The plastic PVA resin is prepared from PVA, plasticizer, surfactant, heat stabilizer, hydrolysis resisting agent, siloxane powder, lubricating agent, melt index regulator, antioxidant and the like. The method comprises the following steps of: weighing the raw materials, adding the raw materials into a high-speed mixer, heating with stirring, and cooling the mixture after the mixture is kept for certain time; and performing granulation, and thus obtaining the plastic PVA resin. The resin is water-soluble resin, can adapt to single-layer or multi-layer membranes or can adapt to injection molding, curtain coating, blow molding and bidirectional stretching, and is a water-soluble membrane series product with cold water solubility and high-temperature water solubility. The method is simple in process, good in processing stability and favorable for continuous production, realizes melting and plastifying extrusion in a dry state, and widens the distance between the melting point and the decomposition point.
Description
Technical field
The invention belongs to the moldable resin field; Be specifically related to plasticity-PVA resin and preparation method thereof.
Background technology
PVA (polyvinyl alcohol) is a kind of well-known broad-spectrum high molecular weight water soluble polymer, the film that this polymkeric substance is made is applied in water transfer printing, embroidery, non-returnable container etc., also have biodegradable, also have various volatile gaseses, gas barrier simultaneously, oil resistant, antistatic, therefore more paid attention to by people, have a large amount of engineering technical personnel to drop into the great effort development research both at home and abroad.The existing temperature range of dry process that adopts is more than 150 ℃, therefore exist condition of high temperature thermooxidative degradation jaundice, crosslinked, mobile poor, volatile gases and flue gas increase, plasticizer extraction phenomenon is difficult to overcome, its quality product is difficult to stable, influence serialization production, at temperature control or too highly cause the gasification generation and can't process.
Summary of the invention
The present invention will solve existing PVA stable resin difference influences the technical problem that serialization is produced; And provide plasticity-PVA resin and preparation method thereof.
Plasticity-PVA resin is by ratio of weight and the number of copies by 50～90 parts of polyvinyl alcohol, 15～45 parts of softening agent in the present embodiment, 0.05～2 parts of tensio-active agents, 0.01～15 parts of thermo-stabilizers, 0.01～1.5 parts of hydrolysis-resisting agents, 0.5～3 part of siloxanes powder, 0.05～5 part of slipping agent, 0.01～0.5 part of melting index conditioning agent, 0.05～5 part of oxidation inhibitor and 0～90 part of starch are made.
The preparation method of plasticity-PVA resin is undertaken by following step in the present embodiment: take by weighing 50～90 parts of polyvinyl alcohol, 15～45 parts of softening agent by ratio of weight and the number of copies, 0.05～2 parts of tensio-active agents, 0.01～15 parts of thermo-stabilizers, 0.01～1.5 parts of hydrolysis-resisting agents, 0.5～3 parts of siloxanes powders, 0.05～5 part of slipping agent, 0.01～0.5 part of melting index conditioning agent, 0.05～5 part of oxidation inhibitor and 0～90 part of starch, add in the high speed mixer then, be heated to 90～120 ℃ while stirring, keep cooling after 10～30 minutes; Place granulation in the dual-screw pelletizer that reverse 90 °, the 45 ° plastic chambeies of screw thread are housed then; Namely obtain plasticity-PVA resin; Wherein extrusion temperature is controlled respectively in 140 °～220 ° scopes, extrude particle and adopt the fervent or air-cooled tie rod of die face, diameter≤2.5mm that die face is fervent, the diameter≤2.5mm of air-cooled tie rod particle and length≤5mm, the length-to-diameter ratio of screw rod (L/D)=40～60: 1.
Described polyvinyl alcohol is selected from that alcoholysis degree 80%～98%, viscosity 20mpa.s～44mpa.s, fugitive constituent≤7, ash≤1.0, pH value are 5～7, the polymerization degree be 1000～2600 and molecular weight be 70000～120000 polyvinyl alcohol.
Described softening agent is to be made through heating by 60～90 parts of primary plasticizers, 10～15 parts of extender plasticizers, 0.1～1.0 part of chainextender and 0.1～0.5 part of rare-earth stabilizer by ratio of quality and the number of copies; Wherein primary plasticizer is a kind of in triethyl citrate, citric acid diethyl ester, acetyl lemon tri-n-butyl, the diethyl glyceryl ester or wherein several combination, extender plasticizer is selected from glycerol, N-butyl phenyl sulphonamide, TriMethylolPropane(TMP), N-ethylbenzene sulphonamide, N-ethyl adjacency pair toluol sulfonamide and phthalyl, chainextender is plastics chain extension agent ADR4370S, and rare-earth stabilizer is the multi-functional composite thermal stabilizer of WWP-R.
Described tensio-active agent is sulfo-succinic acid half diester sodium, polyoxyethylene lauryl ether or the oleic acid diethanolamine that polyoxyethylene glycol, potassium laurate, sulfo-succinic acid ethoxy alcohol half diester disodium, oxyethyl group phenol are derived.
Described thermo-stabilizer is rare earth class thermo-stabilizer, rare earth oxide, Zinic stearas or magnesium hydroxide; Rare earth oxide is La
2O
3, Ce
2O
3, CeO
2, Nd
2O or Praseodymium trioxide, rare earth class thermo-stabilizer are the multi-functional composite thermal stabilizer of WWP-R.
Described hydrolysis-resisting agent is two (2.6 1 diisopropyl phenyl) carbodiimides.
Described slipping agent is a kind of in polyamide wax, polyethylene wax, laurostearic acid glyceride, palmitic acid glyceryl ester, the 18 triglyceride or wherein several combination.
Described oxidation inhibitor is antioxidant 1010, antioxidant 2246, antioxidant 300, phosphorous acid ester or oxidation inhibitor 1035.
Resin of the present invention is water-soluble type resin, and it can adapt in the single or multiple lift film maybe can adapt to all kinds of injection mouldings, curtain coating, blowing, two-way stretch, has the water soluble film series product that cold water is molten, high temperature is water-soluble.
Technology of the present invention is simple; good processing stability; be conducive to serialization production; realize that fusion plastification is extruded under the dry method state; widen fusing point and decomposition point distance; reverse 90 °, the 45 ° plastic chamber of screw thread dual-screw pelletizers are equipped with in use, bring wideer work range and dissimilar particle products thus.The fusing index of product more can adapt to the production of dissimilar device of plastic processing from about the 0.2-2.0, thereby reduces the second investment of processing, can utilize existing plastic apparatus processing fully.The present invention uses rare earth element to overcome polyvinyl alcohol, hydroxyl and a large amount of polyalcohols softening agent and a large amount of hydrogen bonds of producing, reduces insolubles to generate, and reduces degree of crystallinity, is conducive to process for processing, good stability; Introduce a large amount of volatilizations that hydrolysis-resisting agent reduces gas, introduce silicone powder, overcome because polyvinyl alcohol product because inhaling the deliquescing that temperature causes, has improved toughness.Plasticity-PVA resin of the present invention is blown out membrane product, survey performance data, tensile strength is more than 38Mpa, and elongation at break 〉=160%, melting index MI are more than 1.0g/10m, and fusing point is 160～175 ℃, and Vicat softening point is 50～65 ℃, and density is 1.28g/cm
3
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: plasticity-PVA resin is by ratio of weight and the number of copies by 50～90 parts of polyvinyl alcohol, 15～45 parts of softening agent in the present embodiment, 0.05～2 parts of tensio-active agents, 0.01～15 parts of thermo-stabilizers, 0.01～1.5 parts of hydrolysis-resisting agents, 0.5～3 part of siloxanes powder, 0.05～5 part of slipping agent, 0.01～0.5 part of melting index conditioning agent (Dongguan City is moulded logical Science and Technology Ltd.), 0.05～5 part of oxidation inhibitor and 0～90 part of starch are made.
Embodiment two: what present embodiment and embodiment one were different is: plasticity-PVA resin is by ratio of weight and the number of copies by 55～85 parts of polyvinyl alcohol, 20～40 parts of softening agent, 0.1～1 part of tensio-active agent, 0.1～5 parts of thermo-stabilizers, 0.05～1.0 parts of hydrolysis-resisting agents, 0.5～1.5 part of siloxanes powder, 0.1～3.5 part of slipping agent, 0.05～0.1 part of melting index conditioning agent, 0.2～4 part of oxidation inhibitor and 10～80 parts of starch are made.
Embodiment three: what present embodiment was different with embodiment one or two is: described polyvinyl alcohol is selected from that alcoholysis degree 80%～98%, viscosity 20mpa.s～44mpa.s, fugitive constituent≤7, ash≤1.0, pH value are 5～7, the polymerization degree be 1000～2600 and molecular weight be 70000～120000 polyvinyl alcohol (abbreviating PVA as).Other is identical with embodiment one or two.
Present embodiment polyvinyl alcohol mixture can be pressed the arbitrary proportion mixing between the various polyvinyl alcohol trades mark.Polyvinyl alcohol can be the PVA that commercially available prod PVA1788, PVA1799, PVA2088, PVA2099, PVA2499, PVA217, PVA117 etc. meet above-mentioned condition.
Embodiment four: what present embodiment was different with one of embodiment one to three is: described softening agent is to be made through heating by 60～90 parts of primary plasticizers, 10～15 parts of extender plasticizers, 0.1～1.0 part of chainextender and 0.1～0.5 part of rare-earth stabilizer by ratio of quality and the number of copies; Wherein primary plasticizer is a kind of in triethyl citrate, citric acid diethyl ester, acetyl lemon tri-n-butyl, the diethyl glyceryl ester or wherein several combination, extender plasticizer is selected from glycerol, N-butyl phenyl sulphonamide, TriMethylolPropane(TMP), N-ethylbenzene sulphonamide, N-ethyl adjacency pair toluol sulfonamide and phthalyl, chainextender is plastics chain extension agent ADR4370S (BASF Aktiengesellschaft produces), and rare-earth stabilizer is the multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces).Other is identical with one of embodiment one to three.
When the present embodiment primary plasticizer mixes, can mix by any ratio between various primary plasticizers; During the extender plasticizer mixture, can be by any than mixing between various extender plasticizers.
Embodiment five: one of present embodiment and embodiment one to four are not both: described tensio-active agent is sulfo-succinic acid half diester sodium, polyoxyethylene lauryl ether or the oleic acid diethanolamine that polyoxyethylene lauric acid ether, potassium laurate, sulfo-succinic acid ethoxy alcohol half diester disodium, oxyethyl group phenol are derived.Other is identical with one of embodiment one to four.
Embodiment six: what present embodiment was different with one of embodiment one to five is: thermo-stabilizer is rare earth class thermo-stabilizer, rare earth oxide, Zinic stearas or magnesium hydroxide; Rare earth oxide is La
2O
3, Ce
2O
3, CeO
2, Nd
2O or Praseodymium trioxide, rare earth class thermo-stabilizer are the multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces).Other is identical with one of embodiment one to five.
Embodiment seven: what present embodiment was different with one of embodiment one to six is: described hydrolysis-resisting agent is two (2.6 1 diisopropyl phenyl) carbodiimides.Other is identical with one of embodiment one to six.
Embodiment eight: what present embodiment was different with one of embodiment one to seven is: described slipping agent is a kind of in polyamide wax, polyethylene wax, laurostearic acid glyceride, palmitic acid glyceryl ester, the 18 triglyceride or wherein several combination.Other is identical with one of embodiment one to seven.
Oxidation inhibitor is composition in the present embodiment, presses between various oxidation inhibitor arbitrarily than mixing.
Embodiment nine: what present embodiment was different with one of embodiment one to eight is: described oxidation inhibitor is antioxidant 1010, antioxidant 2246, antioxidant 300, phosphorous acid ester or oxidation inhibitor 1035.Other is identical with one of embodiment one to eight.
The described antioxidant 1010 of present embodiment, antioxidant 2246, antioxidant 300 and oxidation inhibitor 1035 all are commercial goods.
Embodiment ten: the preparation method of plasticity-PVA resin is undertaken by following step in the present embodiment: take by weighing 50～90 parts of polyvinyl alcohol by ratio of weight and the number of copies, 15～45 parts of softening agent, 0.05～2 parts of tensio-active agents, 0.01～15 parts of thermo-stabilizers, 0.01～1.5 parts of hydrolysis-resisting agents, 0.5～3 parts of siloxanes powders, 0.05～5 parts of slipping agents, 0.01～0.5 part of melting index conditioning agent (please replenish producer's model), 0.05～5 parts of oxidation inhibitor and 0～90 part of starch, add in the high speed mixer then, be heated to 90～120 ℃ while stirring, keep cooling after 10～30 minutes; Place granulation in the dual-screw pelletizer that reverse 90 °, the 45 ° plastic chambeies of screw thread are housed then; Namely obtain plasticity-PVA resin; Wherein extrusion temperature is controlled respectively in 140 ℃～220 ℃ scopes, extrudes particle and adopts the fervent or air-cooled tie rod of die face, diameter≤2.5mm that die face is fervent, the diameter≤2.5mm of air-cooled tie rod particle and length≤5mm, the length-to-diameter ratio of screw rod=40～60: 1.
Embodiment 11: what present embodiment and embodiment one were different is: take by weighing 55～85 parts of polyvinyl alcohol, 20～40 parts of softening agent by ratio of weight and the number of copies, 0.1～1 part of tensio-active agent, 0.1～5 parts of thermo-stabilizers, 0.05～1.0 parts of hydrolysis-resisting agents, 0.5～1.5 part of siloxanes powder, 0.1～3.5 part of slipping agent, 0.05～0.1 part of melting index conditioning agent, 0.2～4 part of oxidation inhibitor and 10～80 parts of starch.
Embodiment 12: what present embodiment was different with embodiment ten or 11 is: described polyvinyl alcohol is selected from that alcoholysis degree 80%～98%, viscosity 20mpa.s～44mpa.s, fugitive constituent≤7, ash≤1.0, pH value are 5～7, the polymerization degree be 1000～2600 and molecular weight be 70000～120000 polyvinyl alcohol (abbreviating PVA as).Other step is identical with embodiment ten or 11 with parameter.
Present embodiment polyvinyl alcohol mixture can be pressed the arbitrary proportion mixing between the various polyvinyl alcohol trades mark.Polyvinyl alcohol can be the PVA that commercially available prod PVA1788, PVA1799, PVA2088, PVA2099, PVA2499, PVA217, PVA117 etc. meet above-mentioned condition.
Embodiment 13: what present embodiment was different with one of embodiment ten to 12 is: described softening agent is to be made through heating by primary plasticizer, extender plasticizer, chainextender and rare-earth stabilizer; Wherein primary plasticizer is a kind of in triethyl citrate, citric acid diethyl ester, acetyl lemon tri-n-butyl, the diethyl glyceryl ester or wherein several combination, extender plasticizer is selected from glycerol, N-butyl phenyl sulphonamide, TriMethylolPropane(TMP), N-ethylbenzene sulphonamide, N-ethyl adjacency pair toluol sulfonamide and phthalyl, chainextender is plastics chain extension agent ADR4370S (BASF Aktiengesellschaft produces), and rare-earth stabilizer is the multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces).Other step is identical with one of embodiment ten to 12 with parameter.
When the present embodiment softening agent mixes, can mix by any ratio between various primary plasticizers; During the extender plasticizer mixture, can be by any than mixing between various extender plasticizers.
Embodiment 14: one of present embodiment and embodiment ten to 13 are not both: described tensio-active agent is sulfo-succinic acid half diester sodium, polyoxyethylene lauryl ether or the oleic acid diethanolamine that polyoxyethylene lauric acid ether, potassium laurate, sulfo-succinic acid ethoxy alcohol half diester disodium, oxyethyl group phenol are derived.Other step is identical with one of embodiment ten to 13 with parameter.
Embodiment 15: what present embodiment was different with one of embodiment ten to 14 is: thermo-stabilizer is rare earth class thermo-stabilizer, rare earth oxide, Zinic stearas or magnesium hydroxide; Rare earth oxide is La
2O
3, Ce
2O
3, CeO
2, Rb
2O or Praseodymium trioxide, rare earth class thermo-stabilizer are the multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces).Other step is identical with one of embodiment ten to 14 with parameter.
Embodiment 16: what present embodiment was different with one of embodiment ten to 15 is: described hydrolysis-resisting agent is two (2.6 1 diisopropyl phenyl) carbodiimides.Other step is identical with one of embodiment ten to 15 with parameter.
Embodiment 17: what present embodiment was different with one of embodiment ten to 16 is: described slipping agent is a kind of in polyamide wax, polyethylene wax, laurostearic acid glyceride, palmitic acid glyceryl ester, the 18 triglyceride or wherein several combination.Other step is identical with one of embodiment ten to 16 with parameter.
Oxidation inhibitor is composition in the present embodiment, presses between various oxidation inhibitor arbitrarily than mixing.
Embodiment 18: what present embodiment was different with one of embodiment ten to 17 is: described oxidation inhibitor is antioxidant 1010, antioxidant 2246, antioxidant 300, phosphorous acid ester or oxidation inhibitor 1035.Other step is identical with one of embodiment ten to 17 with parameter.
The described antioxidant 1010 of present embodiment, antioxidant 2246, antioxidant 300 and oxidation inhibitor 1035 all are commercial goods.
Embodiment 19: the preparation method of plasticity-PVA resin is undertaken by following step in the present embodiment: take by weighing 67.55 parts of PVA1788 by ratio of weight and the number of copies, 15 parts of softening agent, 0.05 part potassium laurate, 0.2 part multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces), 0.05 part two (2.6 1 diisopropyl phenyl) carbodiimides, 0.5 part siloxanes powder, 1 part of Ployethylene Wax, 0.05 part molten conditioning agent (please replenish producer and model) and 0.2 part of antioxidant 1010 of referring to, add in the high speed mixer then, be heated to 120 ℃ while stirring, keep cooling after 30 minutes; Place granulation in the dual-screw pelletizer that reverse 90 °, the 45 ° plastic chambeies of screw thread are housed then; Namely obtain plasticity-PVA resin; Wherein extrusion temperature is controlled respectively at 200 ℃, extrudes particle and adopts die face fervent, and the fervent diameter of die face is 2.5mm, the length-to-diameter ratio of screw rod=60: 1.
Described softening agent is made through heating by 50 parts of triethyl citrates, 39 parts of acetyl triethyl citrate, 10 parts of vanays, 0.5 part of plastics chain extension agent ADR4370S (BASF Aktiengesellschaft's production) and 0.5 part of rare-earth stabilizer WWP-R03 (Guangdong Weilinna Function Materials Co., Ltd produces); Heating temperature is 110 ℃, and be 3 hours heat-up time.
Plasticity-PVA resin is blown out membrane product, survey performance data, the water-soluble time is 50s/23 ℃ of H
2O (40 μ m blow out under the membrane product and record), recording tensile strength is 39Mpa, elongation at break 〉=160%, melting index MI=1.5g/10m, fusing point are 160 ℃, and Vicat softening point is 57 ℃, and density is 1.28g/cm
3
Embodiment 20: the preparation method of plasticity-PVA resin is undertaken by following step in the present embodiment: take by weighing 67.05 parts of PVA1799 by ratio of weight and the number of copies, 15 parts of softening agent, 0.25 part polyoxyethylene 12 molten basic ethers, 0.2 part multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces), 0.1 part two (2.6 1 diisopropyl phenyl) carbodiimides, 1.0 part siloxanes powder, 1 part of laurostearic acid glyceryl ester, 0.05 part molten conditioning agent (please replenish producer and model) and 0.2 part of antioxidant 2246 of referring to, add in the high speed mixer then, be heated to 120 ℃ while stirring, keep cooling after 30 minutes; Place granulation in the dual-screw pelletizer that reverse 90 °, the 45 ° plastic chambeies of screw thread are housed then; Namely obtain plasticity-PVA resin; Wherein extrusion temperature is controlled respectively at 200 ℃, extrudes particle and adopts die face fervent, and the fervent diameter of die face is 2.5mm, the length-to-diameter ratio of screw rod=55: 1.
Described softening agent is made through heating by 30 parts of triethyl citrates, 30 parts of acetyl triethyl citrate, 15 parts of TriMethylolPropane(TMP)s, 0.5 part of plastics chain extension agent ADR4370S (BASF Aktiengesellschaft's production) and 0.3 part of rare-earth stabilizer WWP-R03 (Guangdong Weilinna Function Materials Co., Ltd produces); Heating temperature is 100 ℃, and be 3 hours heat-up time.
Plasticity-PVA resin is blown out membrane product, survey performance data, the water-soluble time is 80s/80 ℃ of H
2O (40 μ m blow out under the membrane product and record), tensile strength is 38Mpa, elongation at break 〉=180%, melting index MI=1.0g/10m, fusing point are 175 ℃, and Vicat softening point is 51 ℃, and density is 1.28g/cm
3
Embodiment 21: the preparation method of plasticity-PVA resin is undertaken by following step in the present embodiment: take by weighing 66.6 parts of PVA2088 by ratio of weight and the number of copies, 15 parts of softening agent, 0.5 part oleic acid di-alcohol, 0.3 part multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces), 0.2 part two (2.6 1 diisopropyl phenyl) carbodiimides, 0.5 part siloxanes powder, 1 part of palmitic acid glyceryl ester, 0.07 part molten conditioning agent (please replenish producer and model) and 0.5 part of antioxidant 300 of referring to, add in the high speed mixer then, be heated to 120 ℃ while stirring, keep cooling after 30 minutes; Place granulation in the dual-screw pelletizer that reverse 90 °, the 45 ° plastic chambeies of screw thread are housed then; Namely obtain plasticity-PVA resin; Wherein extrusion temperature is controlled respectively at 200 ℃, extrudes particle and adopts air-cooled tie rod, the diameter=2.5mm of air-cooled tie rod particle and length=5mm, the length-to-diameter ratio of screw rod=40～60: 1.
Described softening agent is made through heating by 50 parts of triethyl citrates, 39 parts of acetyl triethyl citrate, 10 parts of vanays, 0.5 part of plastics chain extension agent ADR4370S (BASF Aktiengesellschaft's production) and 0.5 part of rare-earth stabilizer WWP-R03 (Guangdong Weilinna Function Materials Co., Ltd produces); Heating temperature is 110 ℃, and be 3 hours heat-up time.
Plasticity-PVA resin is blown out membrane product, survey performance data, the water-soluble time is 60s/23 ℃ of H
2O (40 μ m blow out under the membrane product and record), tensile strength is 41Mpa, elongation at break 〉=160%, melting index MI=1.8g/10m, fusing point are 165 ℃, and Vicat softening point is 62 ℃, and density is 1.28g/cm
3
Embodiment 22: the preparation method of plasticity-PVA resin is undertaken by following step in the present embodiment: take by weighing 66.6 parts of PVA2099 by ratio of weight and the number of copies, 15 parts of softening agent, 0.5 part oleic acid diethyl ester, 0.3 part multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces), 0.01 part two (2.6 1 diisopropyl phenyl) carbodiimides, 1.0 part siloxanes powder, 1 part of 18 triglyceride, 0.01 part molten conditioning agent (please replenish producer and model) and 0.5 part of phosphorous acid ester of referring to, add in the high speed mixer then, be heated to 120 ℃ while stirring, keep cooling after 30 minutes; Place granulation in the dual-screw pelletizer that reverse 90 °, the 45 ° plastic chambeies of screw thread are housed then; Namely obtain plasticity-PVA resin; Wherein extrusion temperature is controlled respectively at 200 ℃, extrudes particle and adopts die face fervent, diameter≤2.5mm that die face is fervent, the length-to-diameter ratio of screw rod=40～60: 1.
Described softening agent is made through heating by 30 parts of triethyl citrates, 30 parts of acetyl triethyl citrate, 15 parts of TriMethylolPropane(TMP)s, 0.5 part of plastics chain extension agent ADR4370S (BASF Aktiengesellschaft's production) and 0.3 part of rare-earth stabilizer WWP-R03 (Guangdong Weilinna Function Materials Co., Ltd produces); Heating temperature is 100 ℃, and be 3 hours heat-up time.
Plasticity-PVA resin is blown out membrane product, survey performance data, the water-soluble time is 100s/80 ℃ of H20 (40 μ m blow out under the membrane product and record), tensile strength is 44Mpa, elongation at break 〉=200%, melting index MI=1.1g/10m, fusing point are 170 ℃, Vicat softening point is 60 ℃, and density is 1.28g/cm
3
Embodiment 23: the preparation method of plasticity-PVA resin is undertaken by following step in the present embodiment: take by weighing 30 parts of PVA1788 by ratio of weight and the number of copies, 35.5 part PVA1799,15 parts of softening agent, 0.5 part potassium laurate, 0.4 part multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces), 0.1 part two (2.6 1 diisopropyl phenyl) carbodiimides, 2 parts of siloxanes powders, 1 part of polyamide wax, 0.1 molten conditioning agent (please replenish producer and model) and 0.5 part of oxidation inhibitor 1035 of referring to, add in the high speed mixer then, be heated to 120 ℃ while stirring, keep cooling after 30 minutes; Place granulation in the dual-screw pelletizer that reverse 90 °, the 45 ° plastic chambeies of screw thread are housed then; Namely obtain plasticity-PVA resin; Wherein extrusion temperature is controlled respectively at 200 ℃, extrudes particle and adopts die face fervent, diameter≤2.5mm that die face is fervent, the length-to-diameter ratio of screw rod=60: 1.
Described softening agent is made through heating by 50 parts of triethyl citrates, 39 parts of acetyl triethyl citrate, 10 parts of vanays, 0.5 part of plastics chain extension agent ADR4370S (BASF Aktiengesellschaft's production) and 0.5 part of rare-earth stabilizer WWP-R03 (Guangdong Weilinna Function Materials Co., Ltd produces); Heating temperature is 110 ℃, and be 3 hours heat-up time.
Plasticity-PVA resin is blown out membrane product, survey performance data, the water-soluble time is 80s/60 ℃ of H
2O (40 μ m blow out under the membrane product and record) measures elongation at break 〉=180%, and melting index MI=2.5g/10m, fusing point are 165 ℃, and Vicat softening point is 55 ℃, and density is 1.28g/cm
3
Embodiment 24: the preparation method of plasticity-PVA resin is undertaken by following step in the present embodiment: take by weighing 30 parts of PVA1788 by ratio of weight and the number of copies, 35.5 part PVA1799,15 parts of softening agent, 0.5 part potassium laurate, 0.4 part multi-functional composite thermal stabilizer of WWP-R (Guangdong Weilinna Function Materials Co., Ltd produces), 0.1 part two (2.6 1 diisopropyl phenyl) carbodiimides, 2 parts of siloxanes powders, 1 part of polyamide wax, 0.5 part oxidation inhibitor 1035 and 50 parts of starch, add in the high speed mixer then, be heated to 120 ℃ while stirring, keep cooling after 30 minutes; Place granulation in the dual-screw pelletizer that reverse 90 °, the 45 ° plastic chambeies of screw thread are housed then; Namely obtain plasticity-PVA resin; Wherein extrusion temperature is controlled respectively at 200 ℃, extrudes particle and adopts die face fervent, diameter≤2.5mm that die face is fervent, the length-to-diameter ratio of screw rod=60: 1.
Described softening agent is made through heating by 50 parts of triethyl citrates, 39 parts of acetyl triethyl citrate, 10 parts of vanays, 0.5 part of plastics chain extension agent ADR4370S (BASF Aktiengesellschaft's production) and 0.5 part of rare-earth stabilizer WWP-R03 (Guangdong Weilinna Function Materials Co., Ltd produces); Heating temperature is 110 ℃, and be 3 hours heat-up time.
Plasticity-PVA resin is blown out membrane product, survey performance data, the water-soluble time is 80s/60 ℃ of H
2O (40 μ m blow out under the membrane product and record) measures elongation at break 〉=175%, and melting index MI=2.0g/10m, fusing point are 170 ℃, and Vicat softening point is 60 ℃, and density is 1.28g/cm
3
Claims (7)
1. plasticity-PVA resin, it is characterized in that plasticity-PVA resin is by ratio of weight and the number of copies by 50～90 parts of polyvinyl alcohol, 15～45 parts of softening agent, 0.05～2 parts of tensio-active agents, 0.01～15 parts of thermo-stabilizers, 0.01～1.5 parts of hydrolysis-resisting agents, 0.5～3 parts of silicone powders, 0.05～5 parts of slipping agents, 0.01～0.5 part of melting index conditioning agent, 0.05～5 parts of oxidation inhibitor and 0～90 part of starch are made, wherein softening agent is by 60～90 parts of primary plasticizers by ratio of quality and the number of copies, 10～15 parts of extender plasticizers, 0.1～1.0 parts of chainextenders and 0.1～0.5 part of rare-earth stabilizer are made through heating; Wherein primary plasticizer is a kind of in triethyl citrate and the citric acid diethyl ester or wherein several combination, extender plasticizer is selected from glycerol, N-butyl phenyl sulphonamide, TriMethylolPropane(TMP), N-ethylbenzene sulphonamide and N-ethyl adjacency pair toluol sulfonamide, chainextender is plastics chain extension agent ADR4370S, and rare-earth stabilizer is the multi-functional composite thermal stabilizer of WWP-R.
2. plasticity-PVA resin according to claim 1, it is characterized in that plasticity-PVA resin is by ratio of weight and the number of copies by 55～85 parts of polyvinyl alcohol, 20～40 parts of softening agent, 0.1～1 part of tensio-active agent, 0.1～5 parts of thermo-stabilizers, 0.05～1.0 parts of hydrolysis-resisting agents, 0.5～1.5 part of silicone powder, 0.1～3.5 part of slipping agent, 0.05～0.1 part of melting index conditioning agent, 0.2～4 part of oxidation inhibitor and 10～80 parts of starch are made.
3. plasticity-PVA resin according to claim 1 and 2 is characterized in that described tensio-active agent is polyoxyethylene glycol, potassium laurate, polyoxyethylene lauryl ether or oleic acid diethanolamine.
4. plasticity-PVA resin according to claim 3 is characterized in that thermo-stabilizer is rare earth class thermo-stabilizer, rare earth oxide, Zinic stearas or magnesium hydroxide; Rare earth oxide is La
2O
3, Ce
2O
3, CeO
2Or Praseodymium trioxide, the rare earth class thermo-stabilizer is the multi-functional composite thermal stabilizer of WWP-R.
5. plasticity-PVA resin according to claim 4 is characterized in that described slipping agent is a kind of in polyamide wax, polyethylene wax, laurostearic acid glyceryl ester, palmitic acid glyceryl ester, the 18 triglyceride or wherein several combination.
6. plasticity-PVA resin according to claim 5 is characterized in that oxidation inhibitor is antioxidant 1010, antioxidant 2246, antioxidant 300, phosphorous acid ester or oxidation inhibitor 1035.
7. the preparation method of plasticity-PVA resin according to claim 1, the preparation method who it is characterized in that plasticity-PVA resin is undertaken by following step: take by weighing 50～90 parts of polyvinyl alcohol by ratio of weight and the number of copies, 15～45 parts of softening agent, 0.05～2 parts of tensio-active agents, 0.01～15 parts of thermo-stabilizers, 0.01～1.5 parts of hydrolysis-resisting agents, 0.5～3 parts of silicone powders, 0.05～5 parts of slipping agents, 0.01～0.5 part of melting index conditioning agent, 0.05～5 parts of oxidation inhibitor and 0～90 part of starch, add in the high speed mixer then, be heated to 90～120 ℃ while stirring, keep cooling after 10～30 minutes; Place granulation in the dual-screw pelletizer that reverse 90 °, the 45 ° plastic chambeies of screw thread are housed then; Namely obtain plasticity-PVA resin; Wherein extrusion temperature is controlled respectively in 140 °～220 ° scopes, extrudes particle and adopts the fervent or air-cooled tie rod of die face, diameter≤2.5mm that die face is fervent, the diameter≤2.5mm of air-cooled tie rod particle and length≤5mm, the length-to-diameter ratio of screw rod=40～60:1.
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| CN102391598B (en) * | 2011-09-07 | 2013-06-26 | 北京工商大学 | Polyvinyl alcohol material and production method thereof |
| CN103341937A (en) * | 2013-07-17 | 2013-10-09 | 北京化工大学常州先进材料研究院 | Method for preparing water-soluble stretch film |
| CN103469678A (en) * | 2013-09-11 | 2013-12-25 | 北京化工大学常州先进材料研究院 | Preparation method of recyclable coated paper |
| CN103724899A (en) * | 2013-12-30 | 2014-04-16 | 浙江七色鹿色母粒有限公司 | Thermal plasticizing polyvinyl alcohol modified material |
| KR102229234B1 (en) * | 2014-02-06 | 2021-03-17 | 주식회사 쿠라레 | Polyvinyl alcohol film |
| CN103923353B (en) * | 2014-05-07 | 2016-08-24 | 王志刚 | Starch base Dining tool and preparation method thereof |
| CN105295110B (en) * | 2015-11-04 | 2018-07-27 | 南京邮电大学 | A kind of artificial flowers and preparation method thereof with anti-microbial attributes |
| CN109721907B (en) * | 2017-10-30 | 2022-01-04 | 中国石油化工股份有限公司 | Flame-retardant polyvinyl alcohol film, composition and preparation method thereof |
| CN113201196A (en) * | 2021-05-11 | 2021-08-03 | 倪显成 | PVA film and production process thereof |
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| CN101580618A (en) * | 2009-06-24 | 2009-11-18 | 宜兴市高拓高分子材料有限公司 | Polyvinyl alcohol film and preparation method thereof |
| CN102086292A (en) * | 2010-11-26 | 2011-06-08 | 四川大学 | Thermoplastic polyvinyl alcohol-soapstone composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101580618A (en) * | 2009-06-24 | 2009-11-18 | 宜兴市高拓高分子材料有限公司 | Polyvinyl alcohol film and preparation method thereof |
| CN102086292A (en) * | 2010-11-26 | 2011-06-08 | 四川大学 | Thermoplastic polyvinyl alcohol-soapstone composite material and preparation method thereof |
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