CN103408687B - A kind of PVDC composition for PP TYPE - Google Patents
A kind of PVDC composition for PP TYPE Download PDFInfo
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- CN103408687B CN103408687B CN201310301576.7A CN201310301576A CN103408687B CN 103408687 B CN103408687 B CN 103408687B CN 201310301576 A CN201310301576 A CN 201310301576A CN 103408687 B CN103408687 B CN 103408687B
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Abstract
The invention discloses a kind of PVDC composition for PP TYPE, said composition is composed of the following components by weight: pH value dash adjustment agent 0.04 ~ 0.25 part, VDC monomer 88 ~ 95 parts, MA monomer 5 ~ 12 parts, initiator 0.15 ~ 0.55 part, dispersion agent 0.06 ~ 0.25 part, PVDC composition processing characteristics of the present invention is stablized, and obtained multi-layer co-extruded extrusion film face is sparkling and crystal-clear, and transparency is good, and there is excellent barrier property, oxygen permeating amount is less than 12.5cm
3/ (m
224h0.1MPa), permeable amount is less than 1.68g/ (m
224h).
Description
Technical field
The present invention relates to a kind of PVDC composition, in particular, the present invention relates to a kind of VDC/MA copolymerized PVDC composition for PP TYPE.
Background technology
The main ingredient of polyvinylidene dichloride (being called for short PVDC) is vinylidene chloride (VDC), owing to having symmetrical molecular structure and the existence of hydrophobic group chlorine, it is made to have higher crystallinity and fusing point, block water, oxygen resistance is good, and the barrier of gas is not subject to the impact of ambient moisture, be widely used in the fields such as food, medicine, military project.Along with the development of producing and growth in the living standard, the barrier property of people to Plastic Packaging Materials is had higher requirement, especially the packing instructions of the commodity such as food, medicine have higher barrier property, therefore based on the Plastic Packaging Materials of PVDC, particularly PVDC-MA(methyl acrylate) application of multilayer copolymerized compound membrane is more and more extensive.PVDC-MA multilayer copolymerized compound membrane core layer is VDC/MA (vinylidene chloride/methyl acrylate) copolymer composition, VDC/MA copolymer composition adds at blown film and there is poor heat stability man-hour, with other high-temperature fusion resin material (as resins such as PE, EVA) once-combined difficult forming, thus cause the multi-layer co-extruded extrusion film face prepared to whiten, poor transparency, easy decomposition variable color, and then the barrier property affecting continuity and the film produced.Particularly VDC content is higher, during forming process face crystalline substance point more, transparency is poorer, film and other resin bonds also poorer.And reduce the content of VDC in VDC/MA copolymer composition, then thin-film barrier can be caused to be deteriorated.
As WO2011110567A discloses a kind of vinylidene chloride copolymer, it consists of: at least one multipolymer (A) vinylidene chloride and at least one can the comonomers of copolymerization, and monomer is selected from butyl acrylate; (B) polyester deriving from least one aliphaticpolycarboxylic acid and at least one fatty alcohol is selected from.This composition is applicable to single or multiple lift food packaging film.
And for example US Patent No. 2011060071 discloses a kind of vinylidene chloride copolymer.It consists of: (A) at least one vinylidene chloride copolymer, and vinylidene chloride parts by weight are more than 50%, and at least one comonomer, comonomer is selected from vinylformic acid (methacrylic acid), and general molecular structure is CH
2=CR
1cR
2; (B) 0.5-4 part epoxy soybean oil (weight) is added in 100 parts of A; (C) add 0.01-2 part (weight) fluoropolymer in 100 parts of A, fluoropolymer is selected from amorphous fluoropolymer and thinks that its vitrification point is less than or equal to 200 DEG C; (D) the highest 1 part of (weight) acid cleaner in 100 parts of A.The resin made thus can be used for multilayer film.
All there is poor processability in the PVDC-MA resin that above-mentioned patent is produced, obtained multi-layer co-extruded extrusion film face whiting, the problems such as transparency and barrier difference in Multi-layer co-extrusion film-blowing.
Summary of the invention
The technical problem to be solved in the present invention is the defect overcoming prior art, provides a kind of PVDC composition of the multi-layer co-extruded extrusion film good barrier property that processing characteristics is excellent, obtained in Multi-layer co-extrusion film-blowing.
In order to solve the problems of the technologies described above, the present invention is achieved by the following technical solutions:
For a PVDC composition for PP TYPE, said composition is composed of the following components by weight:
The weight-average molecular weight of described PVDC composition is preferably 75000 ~ 90000.
One in the described preferred trisodium phosphate of pH value dash adjustment agent, Sodium Acid Pyrophosphate, Sodium phosphate dibasic and citric acid, its parts by weight are preferably 0.2 part.
One in the special butyl ester of the preferred Diisopropyl azodicarboxylate of described initiator, 2,2'-Azobis(2,4-dimethylvaleronitrile), dilauroyl peroxide, dibenzoyl peroxide and peroxidation-2 ethyl hexanoic acid, its parts by weight are preferably 0.2 part.
One in described dispersion agent preferable methyl Mierocrystalline cellulose, Vltra tears and methyl cellulose ether, its parts by weight are preferably 0.2 part.
The present invention is filled a prescription by aggregation, improve thermostability and the processing characteristics of PVDC composition, during VDC/MA copolymerized PVDC composition of the present invention is applicable to pack for food, middle low-temperature meat product with Multi-layer co-extrusion film-blowing or coextrusion casting film with the material such as nylon, polypropylene, polyethylene, ethylene-vinyl acetate copolymer, be especially suitable for processing PP TYPE.
Weight-average molecular weight (M of the present invention
w) referring to the molecular weight of PVDC composition by molecular wt statistical average, the molecular weight that its value equals often kind of molecule is multiplied by the summation of its weight fraction.Its measuring method can adopt the ordinary method of this area as mensuration such as light scattering method, ultracentrifugal sedimentation tachometric method and gel chromatographies.
The agent of pH value dash adjustment can make the pH value of polymerization system not easily change, pH value dash adjustment agent in the present invention can select the one in trisodium phosphate, Sodium Acid Pyrophosphate and Sodium phosphate dibasic, be preferably trisodium phosphate, its parts by weight are 0.04 ~ 0.25 part, are preferably 0.2 part.
Initiator is heated and can decomposes generation free radical, to cause chain polymerization, initiator in the present invention can select the one in the special butyl ester of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dilauroyl peroxide, dibenzoyl peroxide and peroxidation-2 ethyl hexanoic acid, be preferably the special butyl ester of peroxidation-2 ethyl hexanoic acid, its parts by weight are 0.15 ~ 0.55 part, are preferably 0.2 part.
Dispersion agent can be adsorbed in liquid-solid interface and significantly can reduce interfacial free energy, pressed powder is dispersed in liquid or melt uniformly, and makes it not reassociate.Dispersion agent in the present invention can select the one in methylcellulose gum, Vltra tears and methyl cellulose ether, and be preferably methyl cellulose ether, its parts by weight are 0.06 ~ 0.25 part, is preferably 0.2 part.
Compared with prior art, the present invention has following beneficial effect:
1, filled a prescription by aggregation, improve thermostability and the processing characteristics of PVDC composition, obtained multi-layer co-extruded extrusion film face is sparkling and crystal-clear, and film clarity is good;
2, good with the multi-layer co-extruded extrusion film barrier property that PVDC composition of the present invention is obtained, oxygen permeating amount is less than 12.5cm
3/ (m
224h0.1MPa), permeable amount is less than 1.68g/ (m
224h).
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
Example 1
For a PVDC composition for PP TYPE, its composition of raw materials is as follows:
Preparation process is as follows:
(1) the pH value dash adjustment agent aqueous solution and aqueous dispersant is prepared: by trisodium phosphate 1kg, deionized water 10kg is mixed with the pH value dash adjustment agent aqueous solution; By methyl cellulose ether 1.5kg, deionized water 260kg is mixed with aqueous dispersant;
(2) mix monomer is prepared: 744kgVDC monomer and 56kgMA monomer are mixed, be mixed with mix monomer;
(3) 700kg deionized water, the 11kgPH value dash adjustment agent aqueous solution are joined 3M
3polymeric kettle (band whipping appts stainless steel polymeric kettle, length-to-diameter ratio is 2:1, three leaf anchor formula oars) in, nitrogen replacement 3 times are used after the pressure testing of envelope still, add after vacuumizing prepare mix monomer 160kg, 0.7kg initiator (peroxidation-2 ethyl hexanoic acid special butyl ester), rapid stirring is after 5 minutes, adds 52.3kg aqueous dispersant.Cold dispersion is after 30 minutes, hot water is led to jacket of polymerization under 70rpm mixing speed, be rapidly heated 70 DEG C and start polyreaction, increase mixing speed with 3.5rpm/h speed simultaneously, temperature of reaction is raised with 2.0 DEG C/h speed, remaining mix monomer is added continuously with the speed of 160.0kg/h, initiator 2.8kg is added continuously with the speed of 0.47kg/h, remaining aqueous dispersant is added continuously with the speed of 52.3kg/h, after adding deionized water 304kg continuously with the speed of 50.67kg/h, repolymerization reaction 3h stops polyreaction, vacuum deviates from residual monomer, be cooled to 45 DEG C of dischargings, centrifugal, dry.
Result: polymerization process is steady, without concentrating exothermic phenomenon, obtained white resin, have good stability, viscosity is 1.44, weight-average molecular weight (M
w) be 86365, apparent density 0.87g/cm
3, three order concentration ratios (60 orders, 80 orders, 100 orders) are 91.32%.
Example 2
For a PVDC composition for PP TYPE, its composition of raw materials is as follows:
Preparation method with embodiment 1, result: obtained white resin, have good stability, viscosity is 1.41, weight-average molecular weight (M
w) be 81980, apparent density 0.77g/cm
3, three order concentration ratios (60 orders, 80 orders, 100 orders) are 84.63%.
Example 3
For a PVDC composition for PP TYPE, its composition of raw materials is as follows:
Preparation method with embodiment 1, result: obtained white resin, have good stability, viscosity is 1.42, weight-average molecular weight (M
w) be 83631, apparent density 0.85g/cm
3, three order concentration ratios (60 orders, 80 orders, 100 orders) are 92.99%.
Example 4
For the manufacture of a PVDC composition for PP TYPE, its composition of raw materials is as follows:
Preparation method is with embodiment 1, and result: obtained white resin, better, viscosity is 1.43 to stability, weight-average molecular weight (M
w) be 85006, apparent density 0.82g/cm
3, three order concentration ratios (60 orders, 80 orders, 100 orders) are 82.02%.
Example 5
For a PVDC composition for PP TYPE, its composition of raw materials is as follows:
Preparation method with embodiment 1, result: obtained white resin, have good stability, viscosity is 1.40, weight-average molecular weight (M
w) be 80594, apparent density 0.87g/cm
3, three order concentration ratios (60 orders, 80 orders, 100 orders) are 89.64%.
Example 6
For a PVDC composition for PP TYPE, its composition of raw materials is as follows:
Preparation method is with embodiment 1, and result: obtained white resin, better, viscosity is 1.42 to stability, weight-average molecular weight (M
w) be 83750, apparent density 0.86g/cm
3, three order concentration ratios (60 orders, 80 orders, 100 orders) are 93.42%.
Example 7
For a PVDC composition for PP TYPE, its composition of raw materials is as follows:
Preparation method is with embodiment 1, and result: obtained white resin, better, viscosity is 1.40 to stability, weight-average molecular weight (M
w) be 75260, apparent density 0.84g/cm
3, three order concentration ratios (60 orders, 80 orders, 100 orders) are 68.75%.
Comparative example
For a PVDC composition for PP TYPE, its composition of raw materials is as follows:
Preparation method with embodiment 1, result: obtained pink colour resin, poor stability, viscosity is 1.41, weight-average molecular weight (M
w) be 82362, apparent density 0.87g/cm
3, three order concentration ratios (60 orders, 80 orders, 100 orders) are 90.33%.
The blown film test that the multi-layer co-extruded forcing machine (JHC-12718) that VDC/MA copolymerized PVDC composition embodiment 1 ~ 7 and comparative example obtained is produced at MACRO carries out.Process of the test is as follows:
First respectively the PVDC composition that embodiment 1 ~ 7 and comparative example obtain respectively being taken 50kg joins in the mixing tank of band temperature control system, mixing is preheating to 50 DEG C, successively add 0.1kg stearic amide, 0.45kg epoxy soybean oil ESO, 3kg chlorinatedpolyethylene, 80 DEG C are warmed up to again with the speed of 30 DEG C/h, mix after 1 hour, be down to normal temperature discharging slaking, obtain the copolymerized PVDC-MA resin that slaking is good.
Respectively copolymerized PVDC-MA resin good for the slaking of embodiment 1 ~ 7 and comparative example gained and PE resin, EVA resin are manually added forcing machine respectively again, at the temperature that table 1, table 2 set, resin is transported to same die head through screw rod shearing plasticizing, through vane cooling, propel the price of, steady bubble device surely steeps, and sheerleg stretches, 360 ° of concussion tractions, deflector roll draws film, trimming, finally introduces winder and completes the rolling of test sample film.
Forcing machine machined parameters arranges in table 1, table 2, wherein:
Z
1represent extruder screw first paragraph temperature, Z
2represent extruder screw second segment temperature, Z
3represent extruder screw the 3rd section of temperature, Z
4represent extruder screw the 4th section of temperature.
Table 1 extruder temperature index (unit: DEG C)
| Z 1 | Z 2 | Z 3 | Z 4 | Flange | Adapter |
| 170 | 170 | 170 | 170 | 165 | 165 |
The each layer temperature of table 2 die head and utility appliance temperature (unit: DEG C)
| Sequence number | Title | Unit | Indication range |
| 1 | Adventitia lip | ℃ | 16 |
| 2 | Outer | ℃ | 150 |
| 3 | Outer adhesion coating | ℃ | 155 |
| 4 | Middle layer | ℃ | 155 |
| 5 | Interior adhesion coating | ℃ | 155 |
| 6 | Internal layer | ℃ | 150 |
| 7 | Oil temperature machine 1 | ℃ | 145 |
| 8 | Oil temperature machine 2 | ℃ | 145 |
Multi-layer co-extruded thin-film barrier detected result is in table 3: wherein oxygen permeability presses GB/T19789 execution, and water permeability is pressed GB/T1037 and performed, and transparency is tested by U.S. Oakland transparency meter RT-6000, and face homogeneity is pressed GB/T6672 and performed.
The multi-layer co-extruded thin-film barrier detected result of table 3
Claims (8)
1., for a PVDC composition for PP TYPE, said composition is composed of the following components by weight:
2. the PVDC composition for PP TYPE according to claim 1, is characterized in that the weight-average molecular weight of described PVDC composition is 75000 ~ 90000.
3. the PVDC composition for PP TYPE according to claim 1, is characterized in that described pH value dash adjustment agent parts by weight are 0.2 part.
4. the PVDC composition for PP TYPE according to claim 1, is characterized in that described initiator parts by weight are 0.2 part.
5. the PVDC composition for PP TYPE according to claim 1, is characterized in that described dispersant weight number is 0.2 part.
6. the PVDC composition for PP TYPE according to claim 1, is characterized in that described pH value dash adjustment agent is selected from the one in trisodium phosphate, Sodium Acid Pyrophosphate, Sodium phosphate dibasic and citric acid.
7. the PVDC composition for PP TYPE according to claim 1, is characterized in that described initiator is selected from the one in the special butyl ester of Diisopropyl azodicarboxylate, 2,2'-Azobis(2,4-dimethylvaleronitrile), dilauroyl peroxide, dibenzoyl peroxide and peroxidation-2 ethyl hexanoic acid.
8. the PVDC composition for PP TYPE according to claim 1, is characterized in that described dispersion agent is selected from the one in methylcellulose gum, Vltra tears and methyl cellulose ether.
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| CN103923250B (en) * | 2014-05-06 | 2016-03-30 | 广东顺德顺炎新材料有限公司 | Resin vinylidene chloride-Acrylate-Acrylic class glycidyl ester terpolymer and preparation method thereof |
| CN104927253B (en) * | 2015-05-19 | 2017-01-11 | 浙江衢州巨塑化工有限公司 | Preparation method of PVDC (polyvinyl dichloride) composition for spinning |
| CN108410280B (en) * | 2018-03-02 | 2020-11-13 | 浙江衢州巨塑化工有限公司 | Preparation method of PVDC aqueous emulsion for coating |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560276A (en) * | 2009-05-21 | 2009-10-21 | 浙江巨化股份有限公司电化厂 | VDC/MA copolymerized PVDC composition |
| CN101580563A (en) * | 2009-05-21 | 2009-11-18 | 浙江巨化股份有限公司电化厂 | Preparation method of PVDC composition by VDC/MA copolymerization |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101560276A (en) * | 2009-05-21 | 2009-10-21 | 浙江巨化股份有限公司电化厂 | VDC/MA copolymerized PVDC composition |
| CN101580563A (en) * | 2009-05-21 | 2009-11-18 | 浙江巨化股份有限公司电化厂 | Preparation method of PVDC composition by VDC/MA copolymerization |
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