CN102070860A - Low-migration-separation polyvinyl chloride material and preparation method thereof - Google Patents
Low-migration-separation polyvinyl chloride material and preparation method thereof Download PDFInfo
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- CN102070860A CN102070860A CN2010106129446A CN201010612944A CN102070860A CN 102070860 A CN102070860 A CN 102070860A CN 2010106129446 A CN2010106129446 A CN 2010106129446A CN 201010612944 A CN201010612944 A CN 201010612944A CN 102070860 A CN102070860 A CN 102070860A
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- pvc material
- polyvinyl chloride
- low migration
- migration precipitation
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a low-migration-separation polyvinyl chloride material and a preparation method thereof. The low-migration-separation polyvinyl chloride material comprises the following ingredients in parts by weight: 100 parts of polyvinyl chloride, 0 to 80 parts of plasticizers A, 0 to 50 parts of plasticizers B, 1 to 10 parts of heat stabilizers, 0.5 to 10 parts of organic modified turface, 0.1 to 2 parts of antioxidants and 0.1 to 1 part of lubricating agent. The low-migration-separation polyvinyl chloride material provided by the invention is the organic/inorganic nanometer composite material, has an excellent barrier property and a mechanical property and can meet the requirements in the relevant fields. Meanwhile, the preparation method provided by the invention has a simple process and a lower cost and has wide industrialized prospects.
Description
Technical field
The present invention relates to a kind of pvc material and preparation method thereof.
Background technology
As the polyvinyl chloride of one of five big general-purpose plastics, have cheap, series of advantages such as mechanical property, chemical resistance, fire-retardant, insulation and smooth surface preferably, be widely used in industrial production and daily life every field.
But along with the enhancing gradually of people's environmental consciousness in recent years, the problem that the additive in the PVC goods, especially softening agent are in use easily separated out migration more and more draws attention.Phthalic ester plasticizer is to use maximum class softening agent in the PVC goods, but phthalic acid two (ethylhexyl) ester (DEHP), dibutyl phthalate (DBP), dicyclohexyl phthalate (DCHP), dinoctyl phthalate (DNOP) etc. are biological internal interference element, can disturb the human hormone to secrete, cause the human endocrine system disorders, the long-term accumulation meeting causes distortion, canceration and sudden change in vivo.European Union in 2005 has passed through RoHs environmental protection instruction, has stipulated must not use in toy for children, food product pack etc. directly influence the plastics of HUMAN HEALTH adjacent benzene class softening agent such as DEHP.The solution that provides at present concentrates on the replacement of softening agent, as selects the high score subclass softening agent of nontoxic non-adjacent benzene class softening agent or the difficult relatively migration precipitation of employing.
Japan, some countries of Europe pay attention to advocate in product, use last degradable weathering be called as the environment-friendly type softening agent, as TBC (tributyl citrate) and TOTM (titanic acid ester series), and TBC is by U.S. food management board (FDA) and other many authorized by states, can use in a large number, but these product prices are too high, and enterprise is difficult to digestion.
In the Chinese invention patent (publication number is CN1657563A), the method for utilizing the polyester softening agent to prepare Material for preparing ultralow molecular migrating polyvinl chloride elastomer alloy is disclosed.Though transport property makes moderate progress, the plasticization effect of polyester softening agent is starkly lower than non-adjacent benzene class softening agent commonly used.Similarly, publication number is to have set forth in the patent of CN101555337A with polycarbonate (MPN) plasticized PVC, to reach the low purpose of environment-friendly polyvinyl chloride of separating out of preparation.The same existence separated out property improvement, but the problem that over-all properties descends.
Adjacent benzene class softening agent such as present DEHP are still the plasticizer for polyvinyl chloride of consumption maximum, come from its lower price and good plasticization effect.So it is extremely difficult wanting at short notice to replace with other softening agent adjacent benzene class softening agent such as DEHP.Therefore, this area presses under the prerequisite that does not change conventional plasticizers, prepares the pvc material with low migration precipitation.
Summary of the invention
The object of the present invention is to provide a kind of low migration precipitation pvc material and preparation method thereof, to overcome the above-mentioned defective that prior art exists, to satisfy the needs of relevant field development.
Low migration precipitation pvc material of the present invention comprises the component of following weight part:
100 parts of polyvinyl chloride
0～80 part of plasticizer A
0～50 part of softening agent B
1～10 part of thermo-stabilizer
0.5～10 part of organically modified montmorillonite clay
0.1～2 part in oxidation inhibitor
0.1～1 part of lubricant
The polymerization degree of described polyvinyl chloride is 500～3000;
Preferably, low migration precipitation pvc material of the present invention comprises the component of following weight part:
100 parts of polyvinyl chloride
40～80 parts of plasticizer A
5～40 parts of softening agent B
1～8 part of thermo-stabilizer
0.5～2 part of organically modified montmorillonite clay
0.1～1 part in oxidation inhibitor
0.1～1 part of lubricant
Described plasticizer A is a primary plasticizer, is selected from dibutyl phthalate, dimixo-octyl phthalate or the tritolyl phosphate etc. more than one;
Described softening agent B is an extender plasticizer, is selected from dioctyl sebacate or the epoxy soybean wet goods more than one;
Described thermo-stabilizer is environment-friendly calcium and zinc composite stabilizer, as the CZ113 of Chemtura Corporation;
Described organically modified montmorillonite clay is the montmorillonite that organises and handle.
Preferably, described organically modified montmorillonite clay is the montmorillonite that adopts 16～18 carbon alkylammonium salt modifications, and the interlamellar spacing of organically modified montmorillonite clay is 1.5～3nm, and the method that the preparation method can provide with reference to Chinese patent (03121924.0) specifically comprises the steps:
Montmorillonite and alkylammonium salt are put into homogenizer by weight, and uniform mixing 30 minutes obtains organically modified montmorillonite clay.
The prescription of described preparation organically modified montmorillonite clay following (weight part):
100 parts of montmorillonites
Alkylammonium salt 10-60 part
Described oxidation inhibitor is selected from more than one in phosphorous acid esters or the Hinered phenols antioxidant, as three (nonyl phenol) phosphorous acid ester (1178) or 2, and 6-di-t-butyl-4-cresylol (264) etc.
Described lubricant is lipid acid or stearic acid compound.
The preparation method of described low migration precipitation pvc material comprises the steps:
Each above-mentioned component is put into stirrer by weight ratio mix, with twin screw extruder melt blending extruding pelletization, processing temperature is 110 ℃～130 ℃, can obtain product.
Although do not plan to be confined to theoretic explanation, the mechanism that the present invention program may exist is:
Polynite is the silicate minerals that typically contains laminate structure, and its crystalline structure is to be made of two-layer silicon-oxy tetrahedron and layer of aluminum oxygen octahedra, belongs to 2: 1 type layered silicates, and its thickness is about 1nm.Interlamellar spacing changes between 0.96～2.14nm with the difference of interlayer cation kind.Usually adopt organic ammonium cationoid tensio-active agent that layered silicate is carried out organic modification, improve its with the polymkeric substance affinity in, further enlargement layer spacing.
After polynite process with laminate structure organises and handles, obtain the Organic of nanoscale by the method for melt blending.Nano level montmorillonite layer is dispersed in the polyvinyl chloride matrix, has obtained good barrier performance, produces the crooked route that a small molecules is difficult to pass through, and makes the small molecules that comprises softening agent be difficult to migration precipitation.
Low migration precipitation pvc material of the present invention is a kind of Organic, has excellent barrier and mechanical property concurrently, can satisfy the needs in relevant field.Simultaneously, preparation method provided by the present invention, technology is simple, and cost is lower, has wide industrial prospect.
Embodiment
The preparation method of organically modified montmorillonite clay:
Montmorillonite and alkylammonium salt are put into homogenizer by weight (100: 30), and uniform mixing 30 minutes obtains organically modified montmorillonite clay.
Comparative example 1
According to table 1 prescription that each material is even in stirrer for mixing, with twin screw extruder extruding pelletization behind melt blending under 120 ℃ the temperature, make soft PVC materials.The performance test results sees Table 2.
Comparative example 2
According to table 1 prescription that each material is even in stirrer for mixing, with twin screw extruder extruding pelletization behind melt blending under 120 ℃ the temperature, make polyvinyl chloride/montmorillonite composite material.The performance test results sees Table 2.
The polynite of non-modified dispersed relatively poor in polyvinyl chloride, the mechanical properties decrease that causes meeting material is bigger, and does not reach the effect of obstruct.
Embodiment 1
According to table 1 prescription that each material is even in stirrer for mixing, with twin screw extruder extruding pelletization behind melt blending under 120 ℃ the temperature, make polychloroethylene/organic modified montmorillonite composite material.The performance test results sees Table 2.
The polynite that organises after handling can be dispersed in the polyvinyl chloride with nano level, reaches enhancing, toughness reinforcing effect, and can form effective barrier layer, and aerial volatilization loss rate of matrix material and the migration loss rate in toluene all reduce.
Embodiment 2
According to table 1 prescription each material is mixed in homogenizer,, make polychloroethylene/organic modified montmorillonite composite material with twin screw extruder extruding pelletization behind melt blending under 120 ℃ the temperature.The performance test results sees Table 2.
Increase the addition (1 weight part) of organic modification montmonrillonite, the mechanical property of polyvinyl chloride composite materials and barrier can further increase, and show matrix material and have the good anti-transport property of separating out.
Embodiment 3
According to table 1 prescription each material is mixed in homogenizer,, make polychloroethylene/organic modified montmorillonite composite material with twin screw extruder extruding pelletization behind melt blending under 120 ℃ the temperature.The performance test results sees Table 2.
Further increase the addition of organo montmorillonite, the over-all properties of polyvinyl chloride composite materials descends to some extent.Under the more addition, polynite is difficult to reach uniform dispersion in the polyvinyl chloride matrix, and assembles easily, causes performance decrease.
The prescription of table 1 polyvinyl chloride composite materials (weight part)
| Prescription | Comparative example 1 | Comparative example 2 | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Polyvinyl chloride | 100 | 100 | 100 | 100 | 100 |
| Plasticizer A | 55 | 55 | 55 | 60 | 75 |
| Softening agent B | 5 | 5 | 5 | 8 | 10 |
| Thermo-stabilizer | 1.5 | 1.5 | 1.5 | 1.5 | 1.5 |
| Unmodified polynite | - | 0.5 | - | - | - |
| Organic modification montmonrillonite | - | - | 0.5 | 1 | 2 |
| Oxidation inhibitor | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Lubricant | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
Above-mentioned polyvinyl chloride polymerization degree is 1000;
Above-mentioned plasticizer A is dimixo-octyl phthalate (DEHP);
Above-mentioned softening agent B is an epoxy soybean oil, and molecular weight is about 1000;
Above-mentioned thermo-stabilizer is environment-protecting asepsis calcium, zinc composite stabilizer;
Above-mentioned organic modification montmonrillonite is the polynite after 16～18 carbon alkylammonium salts are handled;
Above-mentioned oxidation inhibitor is 2,6-di-t-butyl-4-cresylol (264);
Above-mentioned lubricant is a stearic acid.
The performance index of table 2 polyvinyl chloride composite materials
Claims (8)
1. low migration precipitation pvc material is characterized in that, comprises the component of following weight part:
100 parts of polyvinyl chloride
0～80 part of plasticizer A
0～50 part of softening agent B
1～10 part of thermo-stabilizer
0.5～10 part of organically modified montmorillonite clay
0.1～2 part in oxidation inhibitor
0.1～1 part of lubricant.
2. low migration precipitation pvc material according to claim 1 is characterized in that the polymerization degree of described polyvinyl chloride is 500～3000.
3. low migration precipitation pvc material according to claim 1 is characterized in that described plasticizer A is selected from more than one in dibutyl phthalate, dimixo-octyl phthalate or the tritolyl phosphate; Described softening agent B is selected from more than one in dioctyl sebacate or the epoxy soybean oil.
4. low migration precipitation pvc material according to claim 1 is characterized in that described thermo-stabilizer is calcium and zinc composite stabilizer.
5. according to each described low migration precipitation pvc material of claim 1～4, it is characterized in that described organically modified montmorillonite clay is the montmorillonite that organises and handle.
6. low migration precipitation pvc material according to claim 5 is characterized in that, described organically modified montmorillonite clay is the montmorillonite that adopts 16～18 carbon alkylammonium salt modifications.
7. low migration precipitation pvc material according to claim 6 is characterized in that described oxidation inhibitor is selected from more than one in phosphorous acid esters or the Hinered phenols antioxidant, and described lubricant is a lipid acid.
8. according to the preparation method of each described low migration precipitation pvc material of claim 1～7, it is characterized in that, comprise the steps: that each above-mentioned component is put into stirrer by weight ratio to mix, with twin screw extruder melt blending extruding pelletization, processing temperature is 110 ℃～130 ℃, can obtain product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106129446A CN102070860A (en) | 2010-12-29 | 2010-12-29 | Low-migration-separation polyvinyl chloride material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010106129446A CN102070860A (en) | 2010-12-29 | 2010-12-29 | Low-migration-separation polyvinyl chloride material and preparation method thereof |
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| Publication Number | Publication Date |
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| CN102070860A true CN102070860A (en) | 2011-05-25 |
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| CN2010106129446A Pending CN102070860A (en) | 2010-12-29 | 2010-12-29 | Low-migration-separation polyvinyl chloride material and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558714A (en) * | 2011-06-24 | 2012-07-11 | 云南鑫乾矿业有限公司 | Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof |
| CN104194210A (en) * | 2014-08-05 | 2014-12-10 | 山东远洋塑胶工业有限公司 | PVC composite modifier and preparation method thereof |
| CN106496857A (en) * | 2016-11-04 | 2017-03-15 | 广东省汕头市质量计量监督检测所 | A kind of bisphenol-A measure standard substance and preparation method thereof |
| CN106519500A (en) * | 2016-11-09 | 2017-03-22 | 广东省汕头市质量计量监督检测所 | Standard substance for phthalic acid ester plasticizer measurement and preparation method of standard substance |
| CN107163439A (en) * | 2017-06-20 | 2017-09-15 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of the low migration PVC nano composite materials of high tenacity |
| CN110669261A (en) * | 2019-11-17 | 2020-01-10 | 刘琴 | Preparation method of composite calcium-zinc stabilizer for plastic pipeline |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461771A (en) * | 2002-05-28 | 2003-12-17 | 中国科学院化学研究所 | Polyvinylchloride modifier and its preparation method and use |
| CN1504506A (en) * | 2002-12-04 | 2004-06-16 | 中国科学院化学研究所 | Desquamation type polyvinyl chloride nanometer composite material and preparing process thereof |
| US20080194736A1 (en) * | 2007-02-13 | 2008-08-14 | Minqiu Lu | PVC nanocomposite manufacturing technology and applications |
-
2010
- 2010-12-29 CN CN2010106129446A patent/CN102070860A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1461771A (en) * | 2002-05-28 | 2003-12-17 | 中国科学院化学研究所 | Polyvinylchloride modifier and its preparation method and use |
| CN1504506A (en) * | 2002-12-04 | 2004-06-16 | 中国科学院化学研究所 | Desquamation type polyvinyl chloride nanometer composite material and preparing process thereof |
| US20080194736A1 (en) * | 2007-02-13 | 2008-08-14 | Minqiu Lu | PVC nanocomposite manufacturing technology and applications |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102558714A (en) * | 2011-06-24 | 2012-07-11 | 云南鑫乾矿业有限公司 | Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof |
| CN102558714B (en) * | 2011-06-24 | 2013-09-18 | 云南鑫乾矿业有限公司 | Polyvinyl chloride/modified nano montmorillonite compound material and preparation method thereof |
| CN104194210A (en) * | 2014-08-05 | 2014-12-10 | 山东远洋塑胶工业有限公司 | PVC composite modifier and preparation method thereof |
| CN106496857A (en) * | 2016-11-04 | 2017-03-15 | 广东省汕头市质量计量监督检测所 | A kind of bisphenol-A measure standard substance and preparation method thereof |
| CN106519500A (en) * | 2016-11-09 | 2017-03-22 | 广东省汕头市质量计量监督检测所 | Standard substance for phthalic acid ester plasticizer measurement and preparation method of standard substance |
| CN107163439A (en) * | 2017-06-20 | 2017-09-15 | 苏州乔纳森新材料科技有限公司 | A kind of preparation method of the low migration PVC nano composite materials of high tenacity |
| CN110669261A (en) * | 2019-11-17 | 2020-01-10 | 刘琴 | Preparation method of composite calcium-zinc stabilizer for plastic pipeline |
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Application publication date: 20110525 |