CN108546373A - A kind of high-performance modified polyvinyl chloride and preparation method thereof - Google Patents
A kind of high-performance modified polyvinyl chloride and preparation method thereof Download PDFInfo
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- CN108546373A CN108546373A CN201810405391.3A CN201810405391A CN108546373A CN 108546373 A CN108546373 A CN 108546373A CN 201810405391 A CN201810405391 A CN 201810405391A CN 108546373 A CN108546373 A CN 108546373A
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- polyvinyl chloride
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08L27/06—Homopolymers or copolymers of vinyl chloride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/32—Phosphorus-containing compounds
- C08K2003/321—Phosphates
- C08K2003/325—Calcium, strontium or barium phosphate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of high-performance modified polyvinyl chloride and preparation method thereof, the high-performance modified polyvinyl chloride, including the following raw material：PVC, partial cross-linked nitrile rubber compound filler, modified polyphosphoric acid calcium, plasticizer, antioxidant, lubricant.The high-performance modified polyvinyl chloride of the present invention compounds filler, modified polyphosphoric acid calcium by the way that partial cross-linked nitrile rubber is added, and by addition, and further equilibrium improves every mechanical property of polyvinyl chloride.
Description
Technical field
The invention belongs to technical field of polymer, and in particular to a kind of high-performance modified polyvinyl chloride and preparation method thereof.
Background technology
Polyvinyl chloride is to realize one of industrialized plastics variety earliest in the world, is a kind of function admirable, cheap
Resins for universal use, have that excellent flame retardancy, corrosion-resistant, wear-resistant, friction coefficient is small, thermal conductivity is low, good seal performance, anti-
Dirt, sound insulation, antidetonation, it is weather-proof the advantages that, have a wide range of applications in building, light industry, agricultural, packaging, the fields such as daily.But it is poly-
Contain a large amount of C-Cl keys in vinyl chloride molecule, there is larger active force between molecule, therefore it is harder, externally show
Certain brittleness, impact strength is poor, in addition, the C-Cl keys in its molecule are easy to slough HCl molecules when heated, is dividing greatly
Unsaturated bond is introduced in subchain, influences the resistance to ag(e)ing and thermal stability of resin, therefore limits the use scope of polyvinyl chloride
And use space.
Therefore, a kind of high-performance modified polyvinyl chloride of urgent need and preparation method thereof.
Invention content
A kind of high-performance modified polyvinyl chloride of present invention offer and preparation method thereof, it is obtained by optimizing component, dosage
Product has the pvc material of excellent mechanical property.
In order to solve the above technical problems, the present invention uses following technical scheme：
A kind of high-performance modified polyvinyl chloride, which is characterized in that as unit of mass parts, including the following raw material：PVC, part are handed over
Join nitrile rubber, compounds filler, modified polyphosphoric acid calcium, plasticizer, antioxidant, lubricant；Described point of crosslinking acrylonitrile butadiene
Gel mass percentage is 40%-60%；Compounding filler is that hollow structure fiber is mixed with hydroxy silicon oil, the modification
Calcium polyphosphate is the calcium polyphosphate that surface modification is carried out by silane coupling agent；The PVC, the quality of partial cross-linked nitrile rubber
Than being 100:15-25.
Further, the high-performance modified polyvinyl chloride, as unit of mass parts, including the following raw material：PVC100
Part, partial cross-linked nitrile rubber 15-25 parts, 5-10 parts of filler, 5-10 parts of modified polyphosphoric acid calcium are compounded, 4-6 parts of plasticizer resists
1-3 parts of oxygen agent, 2-4 parts of lubricant.
Further, the compounding filler is by the way that hollow structure fiber is immersed in ultrasonic vibration 5- in hydroxy silicon oil
It is obtained by filtration after 15min.
Further, the hollow structure fiber is the nylon66 fiber chopped strand that degree of hollowness is 10-20%.
Further, the plasticizer DOP, DOS, DIDP, liquid polyester type.
Further, the compounding mass ratio of calcium polyphosphate and silane coupling agent is 100 in the modified polyphosphoric acid calcium:5-
10。
Further, the antioxidant is antioxidant 1010 or anti-oxidant DLTP.
Further, the lubricant is at least one of calcium stearate, paraffin, polyethylene wax.
A kind of preparation method of above-mentioned high-performance modified polyvinyl chloride, which is characterized in that include the following steps：
（1）PVC is weighed according to a formula, and partial cross-linked nitrile rubber compounds filler, modified polyphosphoric acid calcium, and plasticizer resists
Oxygen agent, lubricant are put into mixer and are stirred 1-3 minutes, obtain mixed raw material；
（2）The mixing product of the mixed raw material of step 2 and step 1 is put into double screw extruder and is reacted, material exists
Residence time 1-2min in machine barrel, obtains reaction product,
（3）Finished product will be obtained after reaction product pelletizing, drying.
Further, each area's temperature of the double screw extruder is as follows：One 180-200 DEG C of area, two 200-220 DEG C of areas,
Three 200-220 DEG C of areas, four 200-220 DEG C of areas, five 200-220 DEG C of areas, six 200-220 DEG C of areas, seven 200-220 DEG C of areas, 8th area
200-220 DEG C, nine 200-220 DEG C of areas, 200-210 DEG C of head.
The invention has the advantages that：
1) present invention, by the way that the partial cross-linked nitrile rubber of certain gel content is added, effectively improves poly- using PVC as matrix
The impact resistance of vinyl chloride, and equilibrium improves other performance, excessive gel content will cause impact resistance to decline,
Too low gel content will lead to other mechanical properties decreases.
2）The present invention is prepared for compounding filler, and modified polyphosphoric acid calcium is as filler body.Compounding filler is hollow fibre
The compound of peacekeeping hydroxy silicon oil, doughnut are added to the impact resistance for greatly promoting resin and other mechanical properties,
The degree of hollowness of doughnut is 10-20%.It is phenomena such as excessively high degree of hollowness will cause mechanical properties decrease to be easy bubble, too low
Degree of hollowness will cause to can not achieve the larger promotion of impact resistance.Pass through the prior compounding of doughnut and hydroxy silicon oil, energy
The trapped air in doughnut is enough effectively removed, prevents from generating the phenomenon that bubbling, while can promote to disperse.By modified poly-
Calcium phosphate has the addition of the inorganic polymer of long-chain, compared with other inorganic fillers, has and greatly improves the whole of polyvinyl chloride
Body rigidity.Filler is compounded, modified polyphosphoric acid calcium adds simultaneously, has the spy of the balanced mechanical property for improving polyvinyl chloride items
Point, the characteristics of overcoming traditional filler partial properties can be brought to deteriorate.
The high-performance modified polyvinyl chloride of the present invention is filled by the way that partial cross-linked nitrile rubber is added, and by the way that compounding is added
Agent, modified polyphosphoric acid calcium, further equilibrium improve every mechanical property of polyvinyl chloride.
Specific implementation mode
For ease of more fully understanding the present invention, it is illustrated by the following examples, these examples belong to the protection of the present invention
Range, but do not limit the scope of the invention.
It is illustrated below by more specific embodiment.
High-performance modified polyvinyl chloride, which is characterized in that as unit of mass parts, including the following raw material：PVC100 parts, portion
Divide 15-25 parts of crosslinking acrylonitrile butadiene, compounds 5-10 parts of filler, 5-10 parts of modified polyphosphoric acid calcium, 4-6 parts of plasticizer, antioxidant
1-3 parts, 2-4 parts of lubricant.
The gel mass percentage of described point of crosslinking acrylonitrile butadiene is 40%-60%.The compounding filler be pass through by
Hollow structure fiber is immersed in hydroxy silicon oil and is obtained by filtration after ultrasonic vibration 5-15min.The hollow structure fiber is hollow
Degree is the nylon66 fiber chopped strand of 10-20%.The plasticizer is DOP.Calcium polyphosphate and silane are even in the modified polyphosphoric acid calcium
The compounding mass ratio for joining agent is 100:5-10.The antioxidant is antioxidant 1010.The lubricant is polyethylene wax.
A kind of preparation method of above-mentioned high-performance modified polyvinyl chloride, which is characterized in that include the following steps：
（1）PVC is weighed according to a formula, and partial cross-linked nitrile rubber compounds filler, modified polyphosphoric acid calcium, and plasticizer resists
Oxygen agent, lubricant are put into mixer and are stirred 1-3 minutes, obtain mixed raw material；
（2）The mixing product of the mixed raw material of step 2 and step 1 is put into double screw extruder and is reacted, material exists
Residence time 1-2min in machine barrel, obtains reaction product, and each area's temperature of the double screw extruder is as follows：One area 180-200
DEG C, two 200-220 DEG C of areas, three 200-220 DEG C of areas, four 200-220 DEG C of areas, five 200-220 DEG C of areas, six 200-220 DEG C of areas, 7th area
200-220 DEG C, eight 200-220 DEG C of areas, nine 200-220 DEG C of areas, 200-210 DEG C of head.
（3）Finished product will be obtained after reaction product pelletizing, drying.
Embodiment 1
High-performance modified polyvinyl chloride, which is characterized in that as unit of mass parts, including the following raw material：PVC100 parts, part is handed over
Join 20 parts of nitrile rubber, compounds 7.5 parts of filler, 7.5 parts of modified polyphosphoric acid calcium, 5 parts of plasticizer, 2 parts of antioxidant, lubricant 3
Part.
The gel mass percentage of described point of crosslinking acrylonitrile butadiene is 50%.The compounding filler is by will be hollow
Structural fibers are immersed in hydroxy silicon oil and are obtained by filtration after ultrasonic vibration 10min.It is 15% that the hollow structure fiber, which is degree of hollowness,
Nylon66 fiber chopped strand.The plasticizer is DOP.The compounding of calcium polyphosphate and silane coupling agent in the modified polyphosphoric acid calcium
Mass ratio is 100:7.5.The antioxidant is antioxidant 1010.The lubricant is polyethylene wax.
A kind of preparation method of above-mentioned high-performance modified polyvinyl chloride, which is characterized in that include the following steps：
（1）PVC is weighed according to a formula, and partial cross-linked nitrile rubber compounds filler, modified polyphosphoric acid calcium, and plasticizer resists
Oxygen agent, lubricant are put into mixer and are stirred 2 minutes, obtain mixed raw material；
（2）The mixing product of the mixed raw material of step 2 and step 1 is put into double screw extruder and is reacted, material exists
Residence time 1-2min in machine barrel, obtains reaction product, and each area's temperature of the double screw extruder is as follows：One area 180-200
DEG C, two 200-220 DEG C of areas, three 200-220 DEG C of areas, four 200-220 DEG C of areas, five 200-220 DEG C of areas, six 200-220 DEG C of areas, 7th area
200-220 DEG C, eight 200-220 DEG C of areas, nine 200-220 DEG C of areas, 200-210 DEG C of head.
（3）Finished product will be obtained after reaction product pelletizing, drying.
Embodiment 2
High-performance modified polyvinyl chloride, which is characterized in that as unit of mass parts, including the following raw material：PVC100 parts, part is handed over
Join 25 parts of nitrile rubber, compounds 5 parts of filler, 10 parts of modified polyphosphoric acid calcium, 4 parts of plasticizer, 3 parts of antioxidant, 2 parts of lubricant.
The gel mass percentage of described point of crosslinking acrylonitrile butadiene is 60%.The compounding filler is by will be hollow
Structural fibers are immersed in hydroxy silicon oil and are obtained by filtration after ultrasonic vibration 5min.It is 20% that the hollow structure fiber, which is degree of hollowness,
Nylon66 fiber chopped strand.The plasticizer is DOP.The compounding of calcium polyphosphate and silane coupling agent in the modified polyphosphoric acid calcium
Mass ratio is 100:5.The antioxidant is antioxidant 1010.The lubricant is polyethylene wax.
Preparation method is same as Example 1.
Embodiment 3
High-performance modified polyvinyl chloride, which is characterized in that as unit of mass parts, including the following raw material：PVC100 parts, part is handed over
Join 15 parts of nitrile rubber, compounds 10 parts of filler, 5 parts of modified polyphosphoric acid calcium, 6 parts of plasticizer, 1 part of antioxidant, 4 parts of lubricant.
The gel mass percentage of described point of crosslinking acrylonitrile butadiene is 40%.The compounding filler is by will be hollow
Structural fibers are immersed in hydroxy silicon oil and are obtained by filtration after ultrasonic vibration 15min.It is 10% that the hollow structure fiber, which is degree of hollowness,
Nylon66 fiber chopped strand.The plasticizer is DOP.The compounding of calcium polyphosphate and silane coupling agent in the modified polyphosphoric acid calcium
Mass ratio is 100:10.The antioxidant is antioxidant 1010.The lubricant is polyethylene wax.
Preparation method is same as Example 1.
Comparative example 1
It is essentially identical with the preparation process of embodiment 1, have only unlike prepares it is scarce in the raw material of high-performance modified polyvinyl chloride
Small part crosslinking acrylonitrile butadiene.
Comparative example 2
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing in the middle part of the raw material of high-performance modified polyvinyl chloride
It is 20% to divide the gel content of crosslinking acrylonitrile butadiene.
Comparative example 3
It is essentially identical with the preparation process of embodiment 1, it has only the difference is that preparing in the middle part of the raw material of high-performance modified polyvinyl chloride
It is 80% to divide the gel content of crosslinking acrylonitrile butadiene.
Comparative example 4
It is essentially identical with the preparation process of embodiment 1, have only unlike prepare sulphur in the raw material of high-performance modified polyvinyl chloride
Lack compounding filler, modified polyphosphoric acid calcium.
Comparative example 5
It is essentially identical with the preparation process of embodiment 1, have only unlike prepares it is scarce in the raw material of high-performance modified polyvinyl chloride
Filler is compounded less.
Comparative example 6
It is essentially identical with the preparation process of embodiment 1, have only unlike prepares it is scarce in the raw material of high-performance modified polyvinyl chloride
Few modified polyphosphoric acid calcium.
Comparative example 7
It is essentially identical with the preparation process of embodiment 1, have only unlike prepares in the raw material of high-performance modified polyvinyl chloride and answers
Doughnut is directly changed into filler.
Comparative example 8
It is essentially identical with the preparation process of embodiment 1, have only unlike prepares in the raw material of high-performance modified polyvinyl chloride and answers
General fibre is directly changed into filler.
Tensile strength presses ASTM D-638 standards, and bending strength presses ASTM D-790 standards, carries out sample preparation test.According to
ISO2039-2 measures Rockwell hardness.Under the conditions of 25 DEG C, impact property is tested.
As seen from the above table：By the data of embodiment 1-3 and comparative example 1-8 as it can be seen that the high-performance modified polychlorostyrene second of the present invention
Alkene compounds filler, modified polyphosphoric acid calcium by the way that partial cross-linked nitrile rubber is added, and by addition, and further equilibrium improves
Every mechanical property of polyvinyl chloride.
The above content is it cannot be assumed that present invention specific implementation is confined to these explanations, for the technical field of the invention
Those of ordinary skill for, under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all answers
When being considered as belonging to present invention scope of patent protection determined by the appended claims.
Claims (10)
1. a kind of high-performance modified polyvinyl chloride, which is characterized in that including the following raw material：PVC, partial cross-linked nitrile rubber are multiple
With filler, modified polyphosphoric acid calcium, plasticizer, antioxidant, lubricant；The gel quality percentage of described point of crosslinking acrylonitrile butadiene contains
Amount is 40%-60%；Compounding filler is that hollow structure fiber is mixed with hydroxy silicon oil, and the modified polyphosphoric acid calcium is to pass through
Silane coupling agent carries out the calcium polyphosphate of surface modification；The mass ratio of the PVC, partial cross-linked nitrile rubber are 100:15-25.
2. high-performance modified polyvinyl chloride according to claim 1, which is characterized in that as unit of mass parts, including such as
Lower raw material：PVC100 parts, partial cross-linked nitrile rubber 15-25 parts, 5-10 parts of filler of compounding, 5-10 parts of modified polyphosphoric acid calcium,
4-6 parts of plasticizer, 1-3 parts of antioxidant, 2-4 parts of lubricant.
3. high-performance modified polyvinyl chloride according to claim 1, which is characterized in that the compounding filler be pass through by
Hollow structure fiber is immersed in hydroxy silicon oil and is obtained by filtration after ultrasonic vibration 5-15min.
4. high-performance modified polyvinyl chloride according to claim 1, which is characterized in that the hollow structure fiber is hollow
Degree is the nylon66 fiber chopped strand of 10-20%.
5. high-performance modified polyvinyl chloride according to claim 1, which is characterized in that the plasticizer DOP, DOS,
DIDP, liquid polyester type.
6. high-performance modified polyvinyl chloride according to claim 1, which is characterized in that poly- phosphorus in the modified polyphosphoric acid calcium
The compounding mass ratio of sour calcium and silane coupling agent is 100:5-10.
7. high-performance modified polyvinyl chloride according to claim 1, which is characterized in that the antioxidant is antioxidant
1010 or anti-oxidant DLTP.
8. high-performance modified polyvinyl chloride according to claim 1, which is characterized in that the lubricant is stearic acid
At least one of calcium, paraffin, polyethylene wax.
9. a kind of preparation method of high-performance modified polyvinyl chloride according to claim 1-8, which is characterized in that including with
Lower step：
（1）PVC is weighed according to a formula, and partial cross-linked nitrile rubber compounds filler, modified polyphosphoric acid calcium, and plasticizer resists
Oxygen agent, lubricant are put into mixer and are stirred 1-3 minutes, obtain mixed raw material；
（2）The mixing product of the mixed raw material of step 2 and step 1 is put into double screw extruder and is reacted, material exists
Residence time 1-2min in machine barrel, obtains reaction product,
（3）Finished product will be obtained after reaction product pelletizing, drying.
10. the preparation method of high-performance modified polyvinyl chloride according to claim 9, which is characterized in that the twin-screw
Each area's temperature of extruder is as follows：One 180-200 DEG C of area, two 200-220 DEG C of areas, three 200-220 DEG C of areas, four 200-220 DEG C of areas,
Five 200-220 DEG C of areas, six 200-220 DEG C of areas, seven 200-220 DEG C of areas, eight 200-220 DEG C of areas, nine 200-220 DEG C of areas, head
200-210℃。
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| CN201810405391.3A CN108546373B (en) | 2018-04-29 | 2018-04-29 | High-performance modified polyvinyl chloride and preparation method thereof |
| CN202110390457.8A CN112898704A (en) | 2018-04-29 | 2018-04-29 | High-performance modified polyvinyl chloride |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045942A (en) * | 2014-07-04 | 2014-09-17 | 芜湖中源赛特管业有限公司 | PVC (polyvinyl chloride) pipe and preparation method thereof |
| CN104356530A (en) * | 2014-09-26 | 2015-02-18 | 青岛桐晟桐橡塑科技有限公司 | Formula of electric-conduction and abrasion-proof plastics |
| CN104861352A (en) * | 2014-12-30 | 2015-08-26 | 殷培花 | Impact modified polyvinyl chloride cable material |
| KR101721801B1 (en) * | 2016-05-17 | 2017-03-30 | 주식회사 호만테크 | Pvc compound composition and preparing method thereof |
| CN107501795A (en) * | 2017-09-06 | 2017-12-22 | 淄博职业学院 | Low temperature resistant polyvinyl chloride soft goods composition and preparation method thereof |
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| JPH0493233A (en) * | 1990-08-08 | 1992-03-26 | Mitsubishi Kasei Vinyl Co | Improvement of permanent compressive strain of polyvinyl chloride-based resin molded article |
| JP3170817B2 (en) * | 1991-07-31 | 2001-05-28 | 株式会社ジェイ・エム・エス | Hollow fiber membrane with improved dispersibility and method for producing the same |
| CN103087438B (en) * | 2011-11-02 | 2015-02-11 | 中国石油化工股份有限公司 | Impact-resistant polyvinyl chloride composition and preparation method thereof |
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2018
- 2018-04-29 CN CN202110390457.8A patent/CN112898704A/en active Pending
- 2018-04-29 CN CN201810405391.3A patent/CN108546373B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104045942A (en) * | 2014-07-04 | 2014-09-17 | 芜湖中源赛特管业有限公司 | PVC (polyvinyl chloride) pipe and preparation method thereof |
| CN104356530A (en) * | 2014-09-26 | 2015-02-18 | 青岛桐晟桐橡塑科技有限公司 | Formula of electric-conduction and abrasion-proof plastics |
| CN104861352A (en) * | 2014-12-30 | 2015-08-26 | 殷培花 | Impact modified polyvinyl chloride cable material |
| KR101721801B1 (en) * | 2016-05-17 | 2017-03-30 | 주식회사 호만테크 | Pvc compound composition and preparing method thereof |
| CN107501795A (en) * | 2017-09-06 | 2017-12-22 | 淄博职业学院 | Low temperature resistant polyvinyl chloride soft goods composition and preparation method thereof |
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| CN112898704A (en) | 2021-06-04 |
| CN108546373B (en) | 2021-05-14 |
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