CN101007881A - Starch and polyvinyl alcohol thermoplastic material preparation method - Google Patents
Starch and polyvinyl alcohol thermoplastic material preparation method Download PDFInfo
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- CN101007881A CN101007881A CNA2007100262269A CN200710026226A CN101007881A CN 101007881 A CN101007881 A CN 101007881A CN A2007100262269 A CNA2007100262269 A CN A2007100262269A CN 200710026226 A CN200710026226 A CN 200710026226A CN 101007881 A CN101007881 A CN 101007881A
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Abstract
The invention relates to a method for preparing starch and polyvinyl alcohol thermoplastic material, comprising putting starch, polyvinyl alcohol, plasticizing agent, compatability modifying agent and other auxiliary agent into high- speed machine, mixing for 5- 10 minutes, and extruding granulate at temperature of 120- 140 Deg. C. The product is characterized by quite good mechanic properties, better water resistance and thermal fusion property.
Description
Technical field
The present invention relates to the preparation method of macromolecular material, specifically is the preparation method of a kind of starch and polyvinyl alcohol thermoplastic material.
Background technology
Starch is a kind of low price as a kind of natural polymer, and source and abundant material thereof also are a kind of inexhaustible renewable resourcess.So along with the continuous consumption of petroleum resources, the utilization of developing renewable resources has important social meaning and economic implications.
Present starch and polyvinyl alcohol (PVA) system are that the research and development technology of main raw material thermoplastic material is a lot, because general common starch is the high polar macromolecule material of a kind of high crystallization, when carrying out blending and modifying with synthetic macromolecule, it is poor to have consistency, defectives such as the performance of processing difficulties and material is not good, especially in starch and polyvinyl alcohol (PVA) co-mixing system, show the defective of material water tolerance extreme difference, defective (as the heat sealability of film) with the heat fusion ability has limited using and applying of this material greatly.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of starch and polyvinyl alcohol thermoplastic material, under the prerequisite that keeps this material fundamental property, the water tolerance and the Re Ke fusion faculty of starch and polyvinyl alcohol thermoplastic material improved,
The preparation method of a kind of starch of the present invention and polyvinyl alcohol thermoplastic material comprises:
Starch, polyvinyl alcohol, softening agent, compatible modifier, other auxiliary agents were mixed in homogenizer 5-10 minute, under temperature 120-140 ℃ with the direct blend extruding pelletization of screw extrusion press;
Described raw materials in part by weight is as follows:
Starch 40-70
Polyvinyl alcohol 15-30
Softening agent 15-40
Compatible modifier 3-8
Other auxiliary agents 0.1-1.0
Above raw material umber summation is 100.
Said components can adopt the general component in this area, and preferred version of the present invention is as follows:
Described granulation mode is with air-cooled fervent.
Described starch is W-Gum or tapioca (flour).
Polyvinyl alcohol is that the commercially available trade mark is 1799 commodity;
Softening agent is ethylene glycol, glycerol, hexylene glycol, low-molecular-weight polyethylene glycol, cellosolve, sorbyl alcohol; Methane amide, methylformamide, ethanamide, hydroxyethyl formamide, trolamine or ethanolamine salt;
Other auxiliary agents are one or more mixtures in stearic acid, hexadecanol, stearyl alcohol, the stearylamide.
Described compatible modifier by vinyl-acetic ester and vinylformic acid and acrylic ester monomer thereof by 20-50: the 80-50 weight ratio is mixed copolymerization and is obtained.
Described acrylic ester monomer adopts one or more in vinyl-acetic ester, vinylformic acid, methacrylic acid, acrylate, the crylic acid hydroxy ester.
More specifically, described compatible modifier is prepared by following method:
(1) adopts letex polymerization, show that with negatively charged ion promoting agent makes emulsifying agent, make polymerization starter with superoxide, the emulsifying agent consumption is the 0.1-1.0% weight of reaction-ure mixture, the polymerization starter consumption is the 0.3-0.6% weight of reaction-ure mixture, temperature of reaction is controlled at 50-80 ℃, reacts 2-4 hour;
(2) emulsion that obtains of step (1) is carried out the breakdown of emulsion precipitation, filter, and washing, drying is ground, and crosses 80 eye mesh screens;
(3) the exsiccant polymer powder that obtains of step (2) is by weight polymer powder: methyl alcohol: sodium hydroxide: water is 1: 2: 0.01: 0.0002 mixes, and handles 1 hour down at 50 ℃, filters, and drying and grinding is crossed 80 eye mesh screens.
The described superoxide of step (1) adopts hydrogen peroxide, ammonium persulphate or Potassium Persulphate, and described negatively charged ion shows that promoting agent adopts sodium lauryl sulphate.
The present invention is by joining compatible modifier starch and polyvinyl alcohol (PVA) co-mixing system, through the direct blend extruding pelletization of forcing machine, obtain a kind of water-tolerant, also possess the starch and polyvinyl alcohol (PVA) thermoplastic material of hot fusion power, this material can be processed into goods with injection molding machine of plastic and forcing machine.
The present invention compared with prior art has following advantage: owing to add compatible modifier, not only the consistency with co-mixing system is good, and the mutual capacitive of each component raw material in can the improvement system, the plasticizing capacity of system is improved and processing characteristics improves; And the starch that obtains and polyvinyl alcohol (PVA) thermoplastic material over-all properties also increase, and particularly the water tolerance of material and fusion performance are greatly improved.
Embodiment
Embodiment 1
By vinyl-acetic ester: methyl acrylate: methacrylic acid is that 42: 55: 3 ratios take by weighing raw material 300 grams, adds in the reactor of the 400 gram pure water that are dissolved with 1% sodium lauryl sulphate logical nitrogen emulsification three minutes; Under nitrogen protection,, reacted 8 hours down in 80 ℃ with the initiator that adds 0.5%.Be cooled under 30 ℃, add the salt solution breakdown of emulsion precipitation that breakdown of emulsion is used.Filter, washing 80 ℃ of vacuum-dryings 4 hours, is ground, and crosses 80 mesh sieves, obtains copolymerization product.
This copolymerization product is mixed by following ratio in reactor: copolymerization product: methyl alcohol: sodium hydroxide: water=1: 2: 0.01: 0.0002, and under 50 ℃, handled 1 hour.Filter, drying and grinding is crossed 80 eye mesh screens.Get the alcoholysis and the hydrolysate (1) of vinyl-acetic ester/acrylate, standby.The preparation of starch/polyvinyl alcohol (PVA) thermoplastic material: W-Gum 1200 grams; Polyvinyl alcohol (1799) 800 grams; The alcoholysis of vinyl-acetic ester/acrylate and hydrolysate (1) 80 gram; Glycerol 300 grams, ethylene glycol 170 grams, methane amide 30 grams, stearyl alcohol 10 grams.
Above-mentioned raw materials mixed 5-10 minute in the homogenizer high speed, direct extruding pelletization in forcing machine, prilling temperature 120-140 ℃.
Contrast with blank sample:
The preparation of blank sample: except that alcoholysis that does not add vinyl-acetic ester/acrylate and hydrolysate, all the other composition of raw materials are the same with embodiment 1 with granulation process.
Blank sample and embodiment 1 pellet are produced standard test specimen 160 ℃ of injection mouldings, blank sample tensile strength: 7.15MPa, embodiment 1 tensile strength: 8.03MPa.Under equivalent environment and condition, blank sample and embodiment 1 sample soak test after 24 hours in cold water: blank sample tensile strength: 2.68MPa; Embodiment 1 tensile strength: 6.36MPa.
Thermosol is made a concerted effort relatively: blank sample and embodiment 1 seal the one end at the film of the 160-180 ℃ of about 450MM of blowing diameter, and leakage has promptly been found in the packed entry of blank sample system, and the embodiment 1 unsettled placement of the 3KG water also anhydrous leakage in 7 days of packing into.
Embodiment 2
Tapioca (flour) 1400 grams; Polyvinyl alcohol (1799) 600 grams; The alcoholysis of vinyl-acetic ester/acrylate and hydrolysate (1) 125 gram; Glycerol 300 grams, sorbyl alcohol 150 grams; Methane amide 50 grams; Stearic acid 10 grams.
Above-mentioned raw materials mixed 5-10 minute in the homogenizer high speed, direct extruding pelletization in forcing machine, prilling temperature 120-140 ℃.
The contrast of embodiment 2 and blank sample:
The preparation of blank sample: except that alcoholysis that does not add vinyl-acetic ester/acrylate and hydrolysate, all the other composition of raw materials are the same with embodiment 2 with granulation process.
Blank sample and embodiment 2 pellets are produced standard test specimen 160 ℃ of injection mouldings, blank sample tensile strength: 6.32MPa, embodiment 1 tensile strength: 7.24MPa.Under equivalent environment and condition, blank sample and embodiment 1 sample soak test after 24 hours in cold water: blank sample has been lost mechanical property; Embodiment 1 still keeps the tensile strength of 4.29MPa.
Embodiment 3
By vinyl-acetic ester: methyl acrylate: Hydroxyethyl acrylate is that 40: 55: 5 ratios take by weighing raw material 300 grams, adds in the reactor of the 400 gram pure water that are dissolved with 1% sodium lauryl sulphate logical nitrogen emulsification three minutes; Under nitrogen protection,, reacted 8 hours down in 80 ℃ with the initiator that adds 0.5%.Be cooled under 30 ℃, add the salt solution breakdown of emulsion precipitation that breakdown of emulsion is used.Filter, washing 80 ℃ of vacuum-dryings 4 hours, is ground, and crosses 80 mesh sieves, obtains copolymerization product.
This copolymerization product is mixed by following ratio in reactor: copolymerization product: methyl alcohol: sodium hydroxide: water=1: 2: 0.01: 0.0002, and under 50 ℃, handled 1 hour.Filter, drying and grinding is crossed 80 eye mesh screens.Get the alcoholysis and the hydrolysate (2) of vinyl-acetic ester/acrylate, standby.
The preparation of starch/polyvinyl alcohol (PVA) thermoplastic material: W-Gum 1300 grams; Polyvinyl alcohol (1799) 700 grams; The alcoholysis of vinyl-acetic ester/acrylate and hydrolysate (2) 100 grams; Glycerol 300 grams; Sorbyl alcohol 160 grams; Ethanamide 40 grams; Stearylamide 5 grams; Hexadecanol 5 grams.
Above-mentioned raw materials mixed 5-10 minute in the homogenizer high speed, direct extruding pelletization in forcing machine, prilling temperature 120-140 ℃.
The contrast of embodiment 3 and blank sample:
The preparation of blank sample: except that alcoholysis that does not add vinyl-acetic ester/acrylate and hydrolysate (2), all the other composition of raw materials are the same with embodiment 3 with granulation process.
With embodiment 3 and blank sample blown film, it is that test out its water-absorbent difference after 24 hours: blank sample water-intake rate is respectively 5.6%, 11.09%, 36.55%, 66.35% in 35%, 55%, 80% and 100% the encloses container that the two film sample is placed into relative humidity respectively; And the film sample of embodiment 3 is respectively 1.43%, 5.22%, 13.56% and 18.87%.
Simultaneously, embodiment 3 shows heat sealability and the heat seal strength more excellent than blank sample.
Claims (6)
1, the preparation method of a kind of starch and polyvinyl alcohol thermoplastic material is characterized in that comprising:
Starch, polyvinyl alcohol, softening agent, compatible modifier, other auxiliary agents were mixed in homogenizer 5-10 minute, under temperature 120-140 ℃ with the direct blend extruding pelletization of screw extrusion press;
Described raw materials in part by weight is as follows:
Starch 40-70
Polyvinyl alcohol 15-30
Softening agent 15-40
Compatible modifier 3-8
Other auxiliary agents 0.1-1.0
Above raw material umber summation is 100.
2, method according to claim 1 is characterized in that described starch is W-Gum or tapioca (flour); Polyvinyl alcohol is that the commercially available trade mark is 1799 commodity; Softening agent is ethylene glycol, glycerol, hexylene glycol, low-molecular-weight polyethylene glycol, cellosolve, sorbyl alcohol; Methane amide, methylformamide, ethanamide, hydroxyethyl formamide, trolamine or ethanolamine salt; Other auxiliary agents are one or more mixtures in stearic acid, hexadecanol, stearyl alcohol, the stearylamide.
3, method according to claim 1 and 2, it is characterized in that described compatible modifier by vinyl-acetic ester and vinylformic acid and acrylic ester monomer thereof by 20-50: the 80-50 weight ratio is mixed copolymerization and is obtained.
4, method according to claim 3 is characterized in that described acrylic ester monomer adopts one or more in vinyl-acetic ester, vinylformic acid, methacrylic acid, acrylate, the crylic acid hydroxy ester.
5, method according to claim 4 is characterized in that comprising the steps:
(1) adopts letex polymerization, show that with negatively charged ion promoting agent makes emulsifying agent, make polymerization starter with superoxide, the emulsifying agent consumption is the 0.1-1.0% weight of reaction-ure mixture, the polymerization starter consumption is the 0.3-0.6% weight of reaction-ure mixture, temperature of reaction is controlled at 50-80 ℃, reacts 2-4 hour;
(2) emulsion that obtains of step (1) is carried out the breakdown of emulsion precipitation, filter, and washing, drying is ground, and crosses 80 eye mesh screens;
(3) the exsiccant polymer powder that obtains of step (2) is by weight polymer powder: methyl alcohol: sodium hydroxide: water is 1: 2: 0.01: 0.0002 mixes, and handles 1 hour down at 50 ℃, filters, and drying and grinding is crossed 80 eye mesh screens.
6, method according to claim 5 is characterized in that the described superoxide of step (1) adopts hydrogen peroxide, ammonium persulphate or Potassium Persulphate, and described negatively charged ion shows that promoting agent adopts sodium lauryl sulphate.
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| CNB2007100262269A CN100547022C (en) | 2007-01-08 | 2007-01-08 | The preparation method of starch and polyvinyl alcohol thermoplastic material |
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| CNB2007100262269A CN100547022C (en) | 2007-01-08 | 2007-01-08 | The preparation method of starch and polyvinyl alcohol thermoplastic material |
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| CN102585485A (en) * | 2012-01-06 | 2012-07-18 | 华南理工大学 | Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof |
| CN103146029A (en) * | 2013-03-08 | 2013-06-12 | 太仓协乐高分子材料有限公司 | Preparation method of biodegradable rice starch plastics |
| CN103496151A (en) * | 2013-10-10 | 2014-01-08 | 长沙理工大学 | Preparation method of nano starch for papermaking coating |
| CN103788552A (en) * | 2012-10-26 | 2014-05-14 | 厦门加岩高分子材料有限公司 | Polyvinyl alcohol blend |
| CN103865106A (en) * | 2014-03-31 | 2014-06-18 | 宋旭 | Biodegradable plastic with high starch content and preparation method of biodegradable plastic |
| CN104109262A (en) * | 2014-06-30 | 2014-10-22 | 安徽巢湖南方膜业有限责任公司 | Thermoplastic starch-polyvinyl alcohol composite plastic film |
| CN104231330A (en) * | 2014-09-12 | 2014-12-24 | 华南理工大学 | Completely-degradable composite material based on solid-phase grafting of bagasse and method for preparing completely-degradable composite material based on solid-phase grafting of bagasse |
| CN105504615A (en) * | 2015-12-25 | 2016-04-20 | 佛山市博维环保材料有限公司 | Quick-cold-water-soluble embroidery bottom liner film with excellent weatherability and preparation method thereof |
| CN105694318A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Biodegradable polyvinyl alcohol thin film |
| CN106366356A (en) * | 2016-08-31 | 2017-02-01 | 朱春英 | Tapioca starch resin and preparation method thereof |
| CN106380632A (en) * | 2016-08-31 | 2017-02-08 | 朱春英 | Starch flow promoter and preparation method thereof |
| CN109161058A (en) * | 2018-08-16 | 2019-01-08 | 华南理工大学 | A kind of starch-based material and its preparation and application with cold water solubles characteristic |
| WO2020021302A1 (en) * | 2018-07-22 | 2020-01-30 | Yaghoubi Ebrahim | Pva bottles; biodegradable and soluble in high temperature water |
| CN110835425A (en) * | 2019-11-11 | 2020-02-25 | 湖南工业大学 | Full-degradable starch-based film packaging material and preparation method thereof |
| CN110862583A (en) * | 2019-11-29 | 2020-03-06 | 湖南工业大学 | Thermoplastic starch and preparation method thereof |
| CN111518318A (en) * | 2020-05-27 | 2020-08-11 | 珠海红塔仁恒包装股份有限公司 | Starch-based biological latex and preparation method and application thereof |
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2007
- 2007-01-08 CN CNB2007100262269A patent/CN100547022C/en not_active Expired - Fee Related
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102585485A (en) * | 2012-01-06 | 2012-07-18 | 华南理工大学 | Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof |
| CN102585485B (en) * | 2012-01-06 | 2014-04-02 | 华南理工大学 | Starch/thermoplastic polyurethane (TPU) composite material with high mechanical property and preparation method thereof |
| CN103788552A (en) * | 2012-10-26 | 2014-05-14 | 厦门加岩高分子材料有限公司 | Polyvinyl alcohol blend |
| CN103788552B (en) * | 2012-10-26 | 2016-12-21 | 厦门加岩高分子材料有限公司 | Polyvinyl alcohol blend |
| CN103146029A (en) * | 2013-03-08 | 2013-06-12 | 太仓协乐高分子材料有限公司 | Preparation method of biodegradable rice starch plastics |
| CN103496151A (en) * | 2013-10-10 | 2014-01-08 | 长沙理工大学 | Preparation method of nano starch for papermaking coating |
| CN103865106A (en) * | 2014-03-31 | 2014-06-18 | 宋旭 | Biodegradable plastic with high starch content and preparation method of biodegradable plastic |
| CN104109262A (en) * | 2014-06-30 | 2014-10-22 | 安徽巢湖南方膜业有限责任公司 | Thermoplastic starch-polyvinyl alcohol composite plastic film |
| CN104109262B (en) * | 2014-06-30 | 2016-04-27 | 安徽巢湖南方膜业有限责任公司 | A kind of thermoplastic starch-polyvinyl alcohol composite plastic film |
| CN104231330A (en) * | 2014-09-12 | 2014-12-24 | 华南理工大学 | Completely-degradable composite material based on solid-phase grafting of bagasse and method for preparing completely-degradable composite material based on solid-phase grafting of bagasse |
| CN105694318A (en) * | 2015-09-18 | 2016-06-22 | 安徽柒柒塑业有限公司 | Biodegradable polyvinyl alcohol thin film |
| CN105504615A (en) * | 2015-12-25 | 2016-04-20 | 佛山市博维环保材料有限公司 | Quick-cold-water-soluble embroidery bottom liner film with excellent weatherability and preparation method thereof |
| CN105504615B (en) * | 2015-12-25 | 2018-03-02 | 佛山市博维环保材料有限公司 | Molten embroidery end liner film of the excellent Rapid cooling of a kind of weatherability and preparation method thereof |
| CN106366356A (en) * | 2016-08-31 | 2017-02-01 | 朱春英 | Tapioca starch resin and preparation method thereof |
| CN106380632A (en) * | 2016-08-31 | 2017-02-08 | 朱春英 | Starch flow promoter and preparation method thereof |
| WO2020021302A1 (en) * | 2018-07-22 | 2020-01-30 | Yaghoubi Ebrahim | Pva bottles; biodegradable and soluble in high temperature water |
| CN109161058A (en) * | 2018-08-16 | 2019-01-08 | 华南理工大学 | A kind of starch-based material and its preparation and application with cold water solubles characteristic |
| CN110835425A (en) * | 2019-11-11 | 2020-02-25 | 湖南工业大学 | Full-degradable starch-based film packaging material and preparation method thereof |
| CN110862583A (en) * | 2019-11-29 | 2020-03-06 | 湖南工业大学 | Thermoplastic starch and preparation method thereof |
| CN111518318A (en) * | 2020-05-27 | 2020-08-11 | 珠海红塔仁恒包装股份有限公司 | Starch-based biological latex and preparation method and application thereof |
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|---|---|
| CN100547022C (en) | 2009-10-07 |
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Assignee: Nanhai Nanhai Foshan Electric Wire Technology Co.,Ltd. Assignor: South China University of Technology Contract record no.: 2011440001059 Denomination of invention: Starch and polyvinyl alcohol thermoplastic material preparation method Granted publication date: 20091007 License type: Exclusive License Open date: 20070801 Record date: 20111129 |
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