CN1597776A - Preparation process for nano composite of polyester / clay - Google Patents
Preparation process for nano composite of polyester / clay Download PDFInfo
- Publication number
- CN1597776A CN1597776A CN 03158984 CN03158984A CN1597776A CN 1597776 A CN1597776 A CN 1597776A CN 03158984 CN03158984 CN 03158984 CN 03158984 A CN03158984 A CN 03158984A CN 1597776 A CN1597776 A CN 1597776A
- Authority
- CN
- China
- Prior art keywords
- clay
- parts
- preparation
- polynite
- hour
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a polyester/clay nano-composite preparing method, inserting polyethylene glycol terephthalate polycondensation catalyst and organic intercalation agent at the same time, to enlarge their space, beneficial to macromolecular chains of polyethylene glycol terephthalate entering into the montmorillonite layers, simultaneously the catalytic reaction centre in the layer, using large amount of polymerization heat to further open them, even dissociating them, for improving montmorillonite dispersive uniformity, and high thermal stability.
Description
Technical field
The present invention relates to the preparation method of a kind of polyethylene terephthalate (PET) matrix material, particularly a kind of preparation method of PET/ clay nanocomposites.
Background technology
PET is a kind of polymkeric substance of high comprehensive performance, be widely used in fields such as fiber, beverage bottle and engineering plastics, but its crystallization velocity is slow, heat-drawn wire is low, drawbacks limit such as barrier properties for gases difference its range of application.Patent CN1272513 at first utilizes alkylammonium salt as intercalator intercalation processing to be carried out in polynite and obtains organic montmorillonoid, organic montmorillonoid is scattered in PET monomer or the performed polymer then, the adding catalyzer carries out in-situ polymerization and prepares the PET/ clay nanocomposites, the purer PET of performance such as the heat-drawn wire of this matrix material, crystallization rate and modulus in flexure significantly improve, but the alkylammonium salt heat decomposition temperature is low, influences the thermostability of this material.Patent US5876812 adds polynite in the transesterify stage, in-situ polymerization prepares the PET/ clay nanocomposites, they utilize the PET/ clay nanocomposites that is obtained to blow bottle, this bottle is significantly improved than conventional P ET bottle to the barrier property of oxygen, but the polynite dispersing uniformity is relatively poor.
Summary of the invention
The objective of the invention is to overcome polyester/clay nano composite material poor heat stability in the past, polynite disperses shortcomings such as even inadequately, a kind of polyester/clay nano composite material preparation method is provided, improve the polynite dispersing uniformity, and this polyester/clay nano composite material has higher thermostability.
The preparation method of polyester/clay nano composite material of the present invention, in weight part, carry out as follows:
(1) with the cationic exchange total volume 0.5～20 part of ethylene glycol that adds 50～500 parts of clay of 50～200meq/100g, 50～150 ℃ of stirrings, be uniformly dispersed;
(2) with 0.01～1 part of polycondensation catalyst stirring and dissolving in 50～150 ℃, 5～200 parts ethylene glycol, add in the above-mentioned slurry, above-mentioned mixed solution stirs 0.5～8 hour after-filtration, washing at 50～150 ℃;
(3) above-mentioned wet polynite is uniformly dispersed in 10～600 parts of water, 0.1～20 parts of organic intercalation agents dissolve the back and add in the polynite aqeous suspension in 10～200 parts of water, 30～100 ℃ are stirred 0.5～8 hour after-filtration, washing, drying, obtain intercalation soil through pulverizing;
(4) 100 parts of ethylene glycol terephthalates (BHET) and 0.5～20 part of intercalation soil are added reactor, being warming up to 180～200 ℃ stirred 0.5～3 hour, adopt the ordinary method polycondensation afterwards, be specially: add 0.05～2 part of additive, be warming up to 240～280 ℃, be decompressed to 1～50Pa aftercondensated 1～5 hour through twice, promptly get the polyester/clay nano composite material.Gained polynite disperse phase is scattered in the PET matrix with 10～100nm yardstick.
Described clay is that a class mineral main component is for containing the layered silicate of 85～95% polynites (MMT).Its unit cell is formed by carrying the layer of aluminum oxygen octahedra secretly in the middle of the two-layer silicon-oxy tetrahedron, connects by shared Sauerstoffatom between the two.The montmorillonite clay internal surface has negative charge, the Na of interlayer absorption
+, Ca
2+, Mg
2+Deng positively charged ion is the interchangeability positively charged ion, can exchange with other metallic cation or the organic cation outside the layer.Clay cation total exchange capacity (CEC) is 50～200meq/100g, is preferably 90～110meq/100g.The clay consumption is 0.5～20 part, is preferably 1～5 part.
Described polycondensation catalyst is antimony acetate, antimonous oxide, butyl (tetra) titanate, titanium potassium oxalate(T.P.O.) etc.
Described organic intercalation agent is organic phosphonium salt, pyridinium salt or water-soluble polymers, as hexadecyl triphenyl bromide phosphine, hexadecyl pyridinium bromide, polyvinyl alcohol, polyethylene pyrrole network alkane ketone etc., its heat decomposition temperature is higher than alkylammonium salt, has improved the thermostability of polyester/clay nano composite material.
Described additive can be stablizer, as phosphoric acid salt, phosphite etc., can also be lubricant, nucleator, tinting material etc.Additive can separately or be used.
Characteristics of the present invention are that PET polycondensation catalyst and organic intercalation agent are inserted in the middle of the montmorillonite layer simultaneously.Organic intercalation agent inserts between cheating engaging layer, enlarged the cheating engaging layer spacing, helping the PET macromolecular chain enters between cheating engaging layer, make the catalyzed reaction center occur in interlayer simultaneously, utilize a large amount of heat of polymerizations that montmorillonite layer is further strutted, even lamella dissociated, improved the polynite dispersing uniformity greatly.
Description of drawings
Fig. 1 is a PET/ clay nanocomposites hot weightless picture
Fig. 2 is a PET/ clay nanocomposites XRD figure
Embodiment
Embodiment 1
With cation exchange capacity is that the polynite 10.0g of 100meq/100g adds ethylene glycol 150g, is heated to 80 ℃, and high-speed stirring, suspension.
0.4g antimony acetate is dissolved in the ethylene glycol that 40g is heated to 80 ℃, solution.This solution is slowly joined in the above-mentioned suspension, stirred 4 hours at 80 ℃, naturally cool to room temperature after, centrifugation must precipitate, spent glycol cleans three times, the cheating engaging layer spacing is expanded as 1.7nm by 1.2nm, and Sb is described
3+Exchanged between cheating engaging layer.
Above-mentioned wet polynite is uniformly dispersed in 200g water, 3.2g dissolving the back in 100g water, hexadecyl triphenyl bromide phosphine adds in the polynite aqeous suspension, 90 ℃ are stirred centrifugation after 4 hours, clean repeatedly with distilled water, until detecting no bromide anion with the 0.1N silver nitrate solution, product is pulverized after drying, gets the organic montmorillonoid powder of required tool catalytic activity, and the cheating engaging layer spacing is further expanded as 2.4nm.
100gBHET and above-mentioned polynite powder 3.0g mix, join in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, treat the whole fusions of BHET after, stirred 1 hour fast, add the 0.2g trimethyl phosphite 99, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 10～15Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly get the PET/ clay nanocomposites after 4 hours, intrinsic viscosity is 0.67dl/g, and initial thermal weight loss temperature is 437.1 ℃ (seeing Fig. 1 b), and the cheating engaging layer spacing is greater than 3nm (seeing Fig. 2 b).
Embodiment 2
With cation exchange capacity is that the polynite 8.0g of 110meq/100g adds ethylene glycol 120g, is heated to 80 ℃, and high-speed stirring, suspension.
0.3g antimony acetate is dissolved in the ethylene glycol that 15g is heated to 80 ℃, solution.This solution is slowly joined in the above-mentioned suspension, stirred 4 hours at 80 ℃, naturally cool to room temperature after, centrifugation must precipitate, spent glycol cleans three times, the cheating engaging layer spacing is expanded as 1.7nm by 1.2nm, and Sb is described
3+Exchanged between cheating engaging layer.
Above-mentioned wet polynite is uniformly dispersed in 200g water, 2.1g the dissolving back adds in the polynite aqeous suspension in the hexadecyl pyridinium bromide 100g water, 90 ℃ are stirred centrifugation after 4 hours, clean repeatedly with distilled water, until detecting no bromide anion with the 0.1N silver nitrate solution, product is pulverized after drying, and the organic montmorillonoid powder cheating engaging layer spacing that gets required tool catalytic activity is further expanded as 2.5nm.
100gBHET and above-mentioned polynite powder 4.0g mix, join in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, treat the whole fusions of BHET after, stirred 1 hour fast, add the 0.2g trimethyl phosphite 99, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 8～12Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly get the PET/ clay nanocomposites after 4 hours, intrinsic viscosity is 0.68dl/g, and the cheating engaging layer spacing is greater than 3nm.
Embodiment 3
With cation exchange capacity is that the polynite 15.0g of 90meq/100g adds ethylene glycol 250g, is heated to 80 ℃, and high-speed stirring, suspension.
0.7g antimony acetate is dissolved in the ethylene glycol that 60g is heated to 80 ℃, solution.This solution is slowly joined in the above-mentioned suspension, stirred 4 hours at 80 ℃, naturally cool to room temperature after, centrifugation must precipitate, spent glycol cleans three times.
Above-mentioned wet polynite is uniformly dispersed in 300g water, 8.0g polyvinylpyrrolidone is dissolved in, and the dissolving back adds in the polynite aqeous suspension in the 100g water, 90 ℃ are stirred centrifugation after 2 hours, clean repeatedly with distilled water, centrifugal products therefrom is the organic montmorillonoid powder of tool catalytic activity, and the cheating engaging layer spacing is further expanded as 3.5nm.
100gBHET and above-mentioned polynite powder 2.0g mix, join in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, treat the whole fusions of BHET after, stirred 40 minutes fast, add the 0.2g trimethyl phosphite 99, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 10～15Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly get the PET/ clay nanocomposites after 4 hours, intrinsic viscosity is 0.65dl/g, and initial thermal weight loss temperature is 442.2 ℃ (seeing Fig. 1 c), tests through XRD, finding has not had diffraction peak below 10 °, illustrates that montmorillonite layer peels off (seeing Fig. 2 c) fully.
Embodiment 4
With cation exchange capacity is that the polynite 10.0g of 100meq/100g adds water 300g, is heated to 80 ℃, and high-speed stirring, suspension.
0.05g titanium potassium oxalate(T.P.O.) is dissolved in the 60g water, gets solution.This solution is slowly joined in the above-mentioned suspension, stirred 4 hours at 80 ℃, naturally cool to room temperature after, centrifugation must precipitate, water cleans three times, the cheating engaging layer spacing is expanded as 1.4nm by 1.2nm, illustrates that titanium potassium oxalate(T.P.O.) is adsorbed between cheating engaging layer.
Above-mentioned wet polynite is uniformly dispersed in 250g water, 3.0g polyvinylpyrrolidone is dissolved in, and the dissolving back adds in the polynite aqeous suspension in the 50g water, 80 ℃ are stirred centrifugation after 2 hours, clean repeatedly with distilled water, centrifugal products therefrom is pulverized after drying, be the organic montmorillonoid powder of tool catalytic activity, the cheating engaging layer spacing is further expanded as 3.5nm.
100gBHET and above-mentioned polynite powder 3.0g mix, join in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, treat the whole fusions of BHET after, stirred 40 minutes fast, add the 0.2g trimethyl phosphite 99, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 8～12Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly get the PET/ clay nanocomposites after 4 hours, intrinsic viscosity is 0.68dl/g, and through the XRD test, discovery has not had diffraction peak below 10 °, illustrates that montmorillonite layer peels off fully.
Comparative Examples 1
With cation exchange capacity is that the polynite 8.0g of 100meq/100g is uniformly dispersed in 200g water, 2.2g dissolving the back in 100g water, cetyl trimethylammonium bromide adds in the polynite aqeous suspension, 80 ℃ are stirred centrifugation after 4 hours, clean repeatedly with distilled water, until detecting no bromide anion with the 0.1N silver nitrate solution, product is pulverized after drying, gets organic montmorillonoid powder cheating engaging layer spacing and further expands as 2.5nm.
100gBHET, 0.032g antimonous oxide and above-mentioned polynite powder 3.0g mix, join in the polycondensation container that is connected with high pure nitrogen, be heated to 200 ℃, treat the whole fusions of BHET after, stirred 1 hour fast, add the 0.2g trimethyl phosphite 99, heat up gradually, when temperature rises to more than 240 ℃, begin to vacuumize, be decompressed to 8～12Pa through twice, after temperature is raised to 280 ℃, keep constant temperature.Continue reaction and promptly getting the PET/ clay nanocomposites after 4 hours, intrinsic viscosity is 0.64dl/g, initial thermal weight loss temperature be 435.0 ℃ (see Fig. 1 a) the cheating engaging layer spacing be that 1.8nm (sees Fig. 2 a).
Claims (5)
1. the preparation method of a polyester/clay nano composite material, in weight part, carry out as follows:
(1) with the cationic exchange total volume 0.5～20 part of ethylene glycol that adds 50～500 parts of clay of 50～200meq/100g, 50～150 ℃ of stirrings, be uniformly dispersed;
(2) with 0.01～1 part of polycondensation catalyst stirring and dissolving in 50～150 ℃, 5～200 parts ethylene glycol, add in the above-mentioned slurry, above-mentioned mixed solution stirs 0.5～8 hour after-filtration, washing at 50～150 ℃;
(3) above-mentioned wet polynite is uniformly dispersed in 10～600 parts of water, 0.1～20 parts of organic intercalation agents dissolve the back and add in the polynite aqeous suspension in 10～200 parts of water, 30～100 ℃ are stirred 0.5～8 hour after-filtration, washing, drying, obtain intercalation soil through pulverizing;
(4) 100 parts of ethylene glycol terephthalates and 0.5～20 part of intercalation soil are added reactor, being warming up to 180～200 ℃ stirred 0.5～3 hour, add 0.05～2 part of additive, be warming up to 240～280 ℃, be decompressed to 1～50Pa aftercondensated 1～5 hour through twice, promptly get the polyester/clay nano composite material.
2. according to the preparation method of claim 1, the cationic exchange total volume that it is characterized in that described clay is 90～110meq/100g, and the clay consumption is 1～5 part.
3. according to the preparation method of claim 1, it is characterized in that described polycondensation catalyst is antimony acetate, antimonous oxide, butyl (tetra) titanate or titanium potassium oxalate(T.P.O.).
4. according to the preparation method of claim 1, it is characterized in that described organic intercalation agent is organic phosphonium salt, pyridinium salt or water-soluble polymers.
5. according to the preparation method of claim 1, it is characterized in that described additive is one or more in stablizer, lubricant, nucleator or the tinting material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03158984 CN1261481C (en) | 2003-09-18 | 2003-09-18 | Preparation process for nano composite of polyester / clay |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03158984 CN1261481C (en) | 2003-09-18 | 2003-09-18 | Preparation process for nano composite of polyester / clay |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597776A true CN1597776A (en) | 2005-03-23 |
| CN1261481C CN1261481C (en) | 2006-06-28 |
Family
ID=34660561
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03158984 Expired - Fee Related CN1261481C (en) | 2003-09-18 | 2003-09-18 | Preparation process for nano composite of polyester / clay |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1261481C (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465226C (en) * | 2005-09-06 | 2009-03-04 | 中国科学院化学研究所 | Polyester/fibrous clay nano composite material, preparation method and application thereof |
| CN101831060A (en) * | 2010-04-09 | 2010-09-15 | 江苏兴业塑化股份有限公司 | Preparation method of high barrier light-proof, preservative and environment-friendly polyester material |
| CN101928448A (en) * | 2010-08-16 | 2010-12-29 | 中国科学技术大学 | Nano composite flame-retardant reinforced polyester engineering plastic and preparation method thereof |
| CN101343405B (en) * | 2008-04-29 | 2011-01-12 | 常利红 | Preparation method for aliphatic polyester/phyllosilicate nano-composite material |
| CN101775126B (en) * | 2009-01-09 | 2011-09-07 | 中国石油天然气股份有限公司 | Polyester polycondensation catalyst, and preparation method and application thereof |
| CN105732961A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of polyethylene glycol terephthalate nano composite material |
| CN105732962A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of polyethylene glycol terephthalate/montmorillonite nano composite material |
| CN107815928A (en) * | 2017-10-24 | 2018-03-20 | 贵州大学 | A kind of preparation method of the fire retardant papers based on two-dimensional nano clay layer |
-
2003
- 2003-09-18 CN CN 03158984 patent/CN1261481C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100465226C (en) * | 2005-09-06 | 2009-03-04 | 中国科学院化学研究所 | Polyester/fibrous clay nano composite material, preparation method and application thereof |
| CN101343405B (en) * | 2008-04-29 | 2011-01-12 | 常利红 | Preparation method for aliphatic polyester/phyllosilicate nano-composite material |
| CN101775126B (en) * | 2009-01-09 | 2011-09-07 | 中国石油天然气股份有限公司 | Polyester polycondensation catalyst, and preparation method and application thereof |
| CN101831060A (en) * | 2010-04-09 | 2010-09-15 | 江苏兴业塑化股份有限公司 | Preparation method of high barrier light-proof, preservative and environment-friendly polyester material |
| CN101928448A (en) * | 2010-08-16 | 2010-12-29 | 中国科学技术大学 | Nano composite flame-retardant reinforced polyester engineering plastic and preparation method thereof |
| CN101928448B (en) * | 2010-08-16 | 2013-03-13 | 中国科学技术大学 | Nano composite flame-retardant reinforced polyester engineering plastic and preparation method thereof |
| CN105732961A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of polyethylene glycol terephthalate nano composite material |
| CN105732962A (en) * | 2014-12-11 | 2016-07-06 | 中国石油天然气股份有限公司 | Preparation method of polyethylene glycol terephthalate/montmorillonite nano composite material |
| CN105732961B (en) * | 2014-12-11 | 2018-06-01 | 中国石油天然气股份有限公司 | Preparation method of polyethylene glycol terephthalate nano composite material |
| CN107815928A (en) * | 2017-10-24 | 2018-03-20 | 贵州大学 | A kind of preparation method of the fire retardant papers based on two-dimensional nano clay layer |
| CN107815928B (en) * | 2017-10-24 | 2020-02-14 | 贵州大学 | Preparation method of flame-retardant paper based on two-dimensional nano clay sheet layer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1261481C (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6225374B1 (en) | Method for preparing silicate-polymer composite | |
| JP3187025B2 (en) | Method for producing conductive polymer nanocomposite | |
| CN1261481C (en) | Preparation process for nano composite of polyester / clay | |
| CN1016677B (en) | The layered metal oxide preparation method who contains the interlevel oxidation thing | |
| EP3487829A1 (en) | Process for the production of geopolymer or geopolymer composite | |
| CN100343166C (en) | Process for preparing bentonite based sodium with high expension performance by drying method | |
| Schnepf et al. | Ga22 [Si (SiMe3) 3] 8: The Largest Atom‐Centered Neutral Main Group Metal Cluster | |
| Yoshimoto et al. | X-ray diffraction studies of intercalation compounds prepared from aniline salts and montmorillonite by a mechanochemical processing | |
| CN1263802C (en) | Polyester/lamellar silicate nano composite material and preparation method thereof | |
| CN101343405B (en) | Preparation method for aliphatic polyester/phyllosilicate nano-composite material | |
| Leone et al. | Poly (styrene)-graft-/rhodamine 6G–fluoromica hybrids: synthesis, characterization and photophysical properties | |
| Bruzaud et al. | Syndiotactic Polystyrene/Organoclay Nanocomposites: Synthesis via In Situ Coordination‐Insertion Polymerization and Preliminary Characterization | |
| CN102321240B (en) | Intercalation preparation method of nylon 6/quaternary phosphonium salt modified montmorillonite nano composite material | |
| CN100537658C (en) | Polyester/clay composite material preparation method | |
| Yin et al. | In‐situ synthesis of poly (ethylene terephthalate)/clay nanocomposites using TiO2/SiO2 sol‐intercalated montmorillonite as polycondensation catalyst | |
| KR20200106524A (en) | Layer separation method of layered silicate | |
| CN1212275C (en) | Method for preparing 3*3 tunnel structured manganese oxide octa hedral molecular sieve | |
| KR20050042880A (en) | The organic modification method of clay minerals for polyesters and the preparation method of polyester nanocomposites having improved properties by using organic modified clay and pristine clay | |
| CN1212347C (en) | Parent material containing high organic montmorillonite, and its prepn. method | |
| CN1282708C (en) | Polyester/laminated silicate nanometer composite materials and preparing method thereof | |
| CN101885790B (en) | Spherical composite catalyst for olefin coordination polymerization and preparation method and use thereof | |
| Prahsarn et al. | Influence of molecular structure of quaternary phosphonium salts on Thai bentonite intercalation | |
| CN100537659C (en) | Method for preparing PET copolymer ester/clay nano composite material | |
| CN1249177C (en) | Solid phase intercalation preparation method of nano montmorillonite and its prepared nano montmorillonite base material | |
| KR100788498B1 (en) | Polyester reactive organo clay and polyester nano-complex thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Zhejiang Chancing Packaging Materials Co., Ltd. Assignor: Institute of Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2007.9.1 to 2013.8.31 contract change Contract record no.: 2008330002319 Denomination of invention: Preparation process for nano composite of polyester / clay Granted publication date: 20060628 License type: Exclusive license Record date: 20081124 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.9.1 TO 2013.8.31; CHANGE OF CONTRACT Name of requester: ZHEJIANG PROVINCE INTEGRITY PACKAGING MATERIALS CO Effective date: 20081124 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20060628 Termination date: 20120918 |