CN1962237A - Polyvinyl alcohol hollow container preparation method - Google Patents
Polyvinyl alcohol hollow container preparation method Download PDFInfo
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- CN1962237A CN1962237A CN 200610022317 CN200610022317A CN1962237A CN 1962237 A CN1962237 A CN 1962237A CN 200610022317 CN200610022317 CN 200610022317 CN 200610022317 A CN200610022317 A CN 200610022317A CN 1962237 A CN1962237 A CN 1962237A
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- polyvinyl alcohol
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Abstract
The invention relates to a method for producing polyvinyl alcohol hollow container, wherein it is characterized in that: it dissolves the modifier with compensated structure to the polyvinyl alcohol at 1-25deals into 20-50deals of deionized water, mixing, adding 50-80deals of polyvinyl alcohol, expanding at 20-60Deg. C, adding additives at 0-5deals, mixing, injection molding at injection device whose thermal treatment temperature is 60-170Deg. C and mould temperature is 10-150Deg. C, into hollow container; thermally processing at 40-250Deg. C or infrared drying for 3-120Deg. C, to improve the crystal degree, or at 20-80Deg. C, using crosslink solution whose density is 0.1-5% to treat it for 1-60min; thermally treating or infrared drying, to obtain the product with better insulated, physical and damp-proof properties.
Description
Technical field
The present invention relates to polyvinyl alcohol hollow container and preparation method thereof.More particularly, the present invention relates to adopt the modifier modification polyvinyl alcohol that complementary structure is arranged with polyvinyl alcohol, prepare the polyvinyl alcohol hollow container of barrier property excellence, belong to polymer processing field by melt-blown.
Background technology
The plastic containers mechanical property is good, light weight, be easy to machine-shaping, is widely used in producing hollow container.But most of plastic containers are relatively poor to the barrier of non-polar solven, in order to improve its barrier, research arranged all both at home and abroad, and the Deng Jian of Hunan University discloses high density polyethylene (HDPE)/nylon 6 high-barrier polymer laminated compound intermingling materials (CN1754908A) as waiting; The Chen Yong of Qilu Petroleum Chemical Corporation Institute of group of China Petrochemical Industry sweet smell etc. discloses the high-obstruction laminated hollow container of a kind of polyethylene/vinyl-ethenol copolymer (CN 1413885A); Chengdu Baisu High Polymer Technology Co., Ltd.'s Liu Xiangyang etc. discloses the fluorination treatment process (CN 1803895A) on a kind of off-line polymer product surface.But said method technology is complicated, equipment price is high, seriously polluted and the goods barriering effect is relatively poor.
Polyvinyl alcohol is a kind of function admirable, broad-spectrum polymer, hollow container prepared therefrom has good mechanical performance, excellent resistance oxygen oil resistance, not dust suction, advantage such as transparent, and have water-soluble and biological degradability under certain condition, in packaging material such as non-polar solven, occupy unique, crucial status.At present, polyvinyl alcohol mainly contains as the application of barrier material: du pont company Wei Nuode hole Ma Ermeila adopts polyolefin and nylon/polyvinyl alcohol blend to prepare stratiform hollow product (US 4950513, CN 1035980A); Liu PC of Mobil Oil Corporation is coated in the polymer matrix film surface with polyvinyl alcohol-vinylamine copolymer, thereby improves its barrier (CN 1226202A); With polyvinyl alcohol as intermediate layer (CN 2649507Y, CN 1663789A) of multilayer extruded product etc.But in these were used, polyvinyl alcohol played the effect that improves other polymer barrier mainly as barrier layer, and addition is lower, and was that the research and development that main body prepares the high barrier hollow container do not appear in the newspapers with the polyvinyl alcohol.This is because polyvinyl alcohol is a crystalline polymer, contain a large amount of hydroxyls in the molecule, can form in a large amount of molecules and intermolecular hydrogen bonding, make its fusing point up to 220-240 ℃, but decomposition temperature is low, 160 ℃ promptly begin the etherificate of dewatering, 200 ℃ begin to decompose, melting process promptly decomposes, no thermoplastic process window, hollow container preparation difficulty.
Summary of the invention
The objective of the invention is to provide a kind of preparation method of polyvinyl alcohol hollow container at the deficiencies in the prior art.Be characterized in adopting the modifier modification polyvinyl alcohol that complementary structure is arranged with polyvinyl alcohol, make it can be in blow molding under the molten condition; Improve goods degree of crystallinity by methods such as heat treatment or infra-red dryings, or handle its degree of cross linking of raising by crosslinking agent, final acquisition has high obstructing performance, mechanical property is excellent and lower-cost hollow barrier container.
The objective of the invention is to realize that by following technical measures wherein said raw material umber is parts by weight except that specified otherwise.
The preparation method of polyvinyl alcohol hollow container:
To there be the modifier of complementary structure to be dissolved in 20～50 parts of deionized waters for 1～25 part with polyvinyl alcohol, stir into homogeneous solution, add 50～80 parts of polyvinyl alcohol again, in 20～60 ℃ of following abundant swellings of temperature, add 0～5 part of auxiliary additive, after mixing, blow molding hollow container on 60～170 ℃ of thermoplastic processing temperatures and 10～150 ℃ of blow moulding equipments of mold temperature, again through 40～250 ℃ of heat treatments of excess temperature or infra-red drying 3～120 minutes, improve goods degree of crystallinity, or under 20～80 ℃ of temperature, through the cross-linking agent solution crosslinking Treatment of over-richness 0.1%～5% after 1～60 minute, heat-treat again or infra-red drying, obtain barrier property, the polyvinyl alcohol hollow container of mechanical property and anti humility performance excellence.
The degree of polymerization of polyvinyl alcohol is 1700～2400, and alcoholysis degree is 92～100%.
Modifier is to contain at least a in aliphatic amino acid, hydramine, acid amides, polyalcohol or the amine salt of two to eight carbon atoms.
Modifier is preferably at least a in glycine, glutamic acid, lysine, aminocaproic acid, monoethanolamine, diethanol amine, triethanolamine, formamide, acetamide, dimethylacetylamide, caprolactam, urea, ethylene glycol, glycerine, butanediol, pentanediol, the triethanolamine salt.
Auxiliary additive is at least a in starch, collagen, cellulose, polyacrylate, poly-hexylene glycol, polyethylene glycol oxide, polyacrylamide, polyacrylic acid, Ployethylene Wax, benzoic acid, pentaerythrite, organosiloxane, odium stearate, talcum powder, calcium carbonate, illiteracy holder soil, clay, vermiculite, silica, titanium dioxide, the zinc oxide.
The thermoplastic processing method is the extrusion-blown modling method, extrude stretch-blow method, injection blow molding method, injection drawing blow method, blow-up ratio 1～3, draw ratio 1～3.
Crosslinking agent is boric acid, borax, benzenediol, 2,4-dihydroxy-benzoic acid, any in dimethyl urea, trimethyl melamine, dimethyl ethyl urea, bichromate, organic titanate, formaldehyde, butyraldehyde or the glutaraldehyde.
Prepare the polyvinyl alcohol hollow container as stated above.
The present invention has following advantage:
1. there is the modifier of complementary structure to realize the melt-blown moulding of polyvinyl alcohol by adding, preparation polyvinyl alcohol hollow container with polyvinyl alcohol;
2. gained swelling material can be directly used in the melt-blown moulding, need not extruding pelletization;
3. modifier and auxiliary additive evenly disperse in polyvinyl alcohol, and stable existence is difficult for separating out, and need not to remove, and can improve the impact flexibility and the transparency of container;
4. container has excellent barrier property, mechanical property and resistance to water soak;
5. the present invention need not multi-layer co-extruded, surface-coated and sulfonation and complicated technology such as fluoridizes and improve the container barrier property, and technology is simple, and is easy to operate, and cost is low, is easy to realize suitability for industrialized production.
The specific embodiment
Below by embodiment the present invention is specifically described.Be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as the restriction to the invention protection domain, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to the invention described above content.
Embodiment:
1. the aminocaproic acid with 1kg ethylene glycol, 0.1kg is dissolved in the 20kg deionized water, is mixed into homogeneous solution, adds the degree of polymerization 1750 again, the polyvinyl alcohol 50kg of alcoholysis degree 99mol%, under stirring action in 20 ℃ of following swellings of temperature.Fusion plastification extruded parisons in temperature 60-125 ℃ extruder, behind the axial tension 1.5, in 10 ℃ of moulds of temperature, be blow molded into container, blow-up ratio 3, with 5% organic titanate solution in 80 ℃ of crosslinking Treatment of temperature after 1 minute, 200 ℃ of following heat treatments of temperature 3 minutes.
2. 15kg butanediol, 10kg triethanolamine salt are dissolved in the 50kg deionized water, be mixed into homogeneous solution, add the degree of polymerization 1700 again, the polyvinyl alcohol 80kg of alcoholysis degree 92mol%, under stirring action,, add 3.5kg Tissuemat E, 1kg polyacrylate, 0.5kg calcium sulfate again and mix in 60 ℃ of following swellings of temperature.On injection machine, be blow molded into hollow container, injection temperature 110-130 ℃, 60 ℃ of mold temperatures, blow-up ratio 2.5.With 3% formalin in 60 ℃ of crosslinking Treatment of temperature after 60 minutes, 100 ℃ of heat treatments of temperature 120 minutes.
3. 10kg triethanolamine, 1.5kg glycerine, 1kg caprolactam are dissolved in the 35kg deionized water, be mixed into homogeneous solution, add the degree of polymerization 2400 again, the polyvinyl alcohol 65kg of alcoholysis degree 99mol%, under stirring action,, add 0.5kg polyethylene glycol, 0.5kg vermiculite and 0.05kg silica again and mix in 40 ℃ of following swellings of temperature.In temperature 150-170 ℃ injection blow molding machine parison, behind 1.8 times of the axial tensions, in 150 ℃ of moulds of temperature, be blow molded into container, blow-up ratio 1.5.After 10 minutes, use infra-red drying 3 minutes, 250 ℃ of temperature in 40 ℃ of crosslinking Treatment of temperature with 0.1% borax soln.
Claims (8)
1, the preparation method of polyvinyl alcohol hollow container, it is characterized in that this method contains following steps: will have the modifier of complementary structure to be dissolved in 20～50 parts of deionized waters for 1～25 part with polyvinyl alcohol, stir into homogeneous solution, add 50～80 parts of polyvinyl alcohol again, in 20～60 ℃ of following abundant swellings of temperature, add 0～5 part of auxiliary additive, after mixing, blow molding hollow container on 60～170 ℃ of thermoplastic processing temperatures and 10～150 ℃ of blow moulding equipments of mold temperature, again through 40～250 ℃ of heat treatments of excess temperature or infra-red drying 3～120 minutes, improve goods degree of crystallinity, or under 20～80 ℃ of temperature,, heat-treat again or infra-red drying after 1～60 minute through the cross-linking agent solution crosslinking Treatment of over-richness 0.1%～5%, obtain barrier property, the polyvinyl alcohol hollow container of mechanical property and anti humility performance excellence.
2, according to the preparation method of the described polyvinyl alcohol hollow container of claim 1, the degree of polymerization that it is characterized in that polyvinyl alcohol is 1700～2400, and alcoholysis degree is 92～100%.
3,, it is characterized in that modifier is to contain at least a in aliphatic amino acid, hydramine, acid amides, polyalcohol and the amine salt of two to eight carbon atoms according to the preparation method of the described polyvinyl alcohol hollow container of claim 1.
4,, it is characterized in that modifier is at least a in glycine, glutamic acid, lysine, aminocaproic acid, monoethanolamine, diethanol amine, triethanolamine, formamide, acetamide, dimethylacetylamide, caprolactam, urea, ethylene glycol, glycerine, butanediol, pentanediol, the triethanolamine salt according to the preparation method of the described polyvinyl alcohol hollow container of claim 1.
5,, it is characterized in that auxiliary additive is at least a in starch, collagen, cellulose, polyacrylate, polyethylene glycol, polyethylene glycol oxide, polyacrylamide, polyacrylic acid, Ployethylene Wax, benzoic acid, pentaerythrite, organosiloxane, odium stearate, talcum powder, calcium carbonate, illiteracy holder soil, clay, vermiculite, silica, titanium dioxide, the zinc oxide according to the preparation method of the described polyvinyl alcohol hollow container of claim 1.
6,, it is characterized in that the thermoplastic processing method is the extrusion-blown modling method, extrudes stretch-blow method, injection blow molding method, injection drawing blow method, blow-up ratio 1～3, draw ratio 1～3 according to the preparation method of the described polyvinyl alcohol hollow container of claim 1.
7, according to the preparation method of the described polyvinyl alcohol hollow container of claim 1, it is characterized in that crosslinking agent is boric acid, borax, benzenediol, 2, the 4-dihydroxy-benzoic acid, any in dimethyl urea, trimethyl melamine, dimethyl ethyl urea, bichromate, organic titanate, formaldehyde, butyraldehyde or the glutaraldehyde.
8, prepare the polyvinyl alcohol hollow container according to the described method of claim 1.
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| CNB2006100223170A CN100553940C (en) | 2006-11-24 | 2006-11-24 | The preparation method of polyvinyl alcohol hollow container |
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| CN100553940C CN100553940C (en) | 2009-10-28 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153089B (en) * | 2007-09-06 | 2010-12-01 | 四川大学 | Polyvinyl alcohol polarity sponge plastics and method of producing the same |
| CN101508746B (en) * | 2009-03-19 | 2012-02-08 | 康智勇 | Graft polyvinyl alcohol, composition, product and their preparation methods |
| CN102613019A (en) * | 2011-01-28 | 2012-08-01 | 昆勤清洁用品(昆山)有限公司 | Planting container structure with water retention function |
| CN103443168A (en) * | 2011-03-30 | 2013-12-11 | 可乐丽股份有限公司 | Process for producing ethylene/vinyl alcohol copolymer resin, ethylene/vinyl alcohol copolymer resin, and multilayer structure |
| CN104530618A (en) * | 2014-12-30 | 2015-04-22 | 桐城市福润包装材料有限公司 | Polyvinyl alcohol-based coating preservation packaging material and preparation method thereof |
| US9416208B2 (en) | 2011-03-30 | 2016-08-16 | Kuraray Co., Ltd. | Method for producing ethylene-vinyl alcohol copolymer resin, ethylene-vinyl alcohol copolymer resin, and laminate |
| CN108422721A (en) * | 2018-03-16 | 2018-08-21 | 思必康（厦门）新材料有限公司 | A kind of PVA composite plastics |
| CN110936584A (en) * | 2019-10-18 | 2020-03-31 | 安徽瑞鸿新材料科技有限公司 | Processing method of polyvinyl alcohol hollow container |
-
2006
- 2006-11-24 CN CNB2006100223170A patent/CN100553940C/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101153089B (en) * | 2007-09-06 | 2010-12-01 | 四川大学 | Polyvinyl alcohol polarity sponge plastics and method of producing the same |
| CN101508746B (en) * | 2009-03-19 | 2012-02-08 | 康智勇 | Graft polyvinyl alcohol, composition, product and their preparation methods |
| CN102613019A (en) * | 2011-01-28 | 2012-08-01 | 昆勤清洁用品(昆山)有限公司 | Planting container structure with water retention function |
| CN103443168A (en) * | 2011-03-30 | 2013-12-11 | 可乐丽股份有限公司 | Process for producing ethylene/vinyl alcohol copolymer resin, ethylene/vinyl alcohol copolymer resin, and multilayer structure |
| US9416208B2 (en) | 2011-03-30 | 2016-08-16 | Kuraray Co., Ltd. | Method for producing ethylene-vinyl alcohol copolymer resin, ethylene-vinyl alcohol copolymer resin, and laminate |
| CN104530618A (en) * | 2014-12-30 | 2015-04-22 | 桐城市福润包装材料有限公司 | Polyvinyl alcohol-based coating preservation packaging material and preparation method thereof |
| CN108422721A (en) * | 2018-03-16 | 2018-08-21 | 思必康（厦门）新材料有限公司 | A kind of PVA composite plastics |
| CN110936584A (en) * | 2019-10-18 | 2020-03-31 | 安徽瑞鸿新材料科技有限公司 | Processing method of polyvinyl alcohol hollow container |
| CN110936584B (en) * | 2019-10-18 | 2021-07-20 | 安徽瑞鸿新材料科技有限公司 | Processing method of polyvinyl alcohol hollow container |
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| CN100553940C (en) | 2009-10-28 |
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