CN115466471A - High-fluidity flame-retardant PVC material and preparation method thereof - Google Patents
High-fluidity flame-retardant PVC material and preparation method thereof Download PDFInfo
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- CN115466471A CN115466471A CN202211282018.6A CN202211282018A CN115466471A CN 115466471 A CN115466471 A CN 115466471A CN 202211282018 A CN202211282018 A CN 202211282018A CN 115466471 A CN115466471 A CN 115466471A
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 81
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000000463 material Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920005989 resin Polymers 0.000 claims abstract description 49
- 239000011347 resin Substances 0.000 claims abstract description 49
- 239000003381 stabilizer Substances 0.000 claims abstract description 32
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 29
- 239000004014 plasticizer Substances 0.000 claims abstract description 28
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 27
- 239000000314 lubricant Substances 0.000 claims abstract description 26
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 25
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 22
- 229960001545 hydrotalcite Drugs 0.000 claims description 22
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 22
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 claims description 21
- 239000004114 Ammonium polyphosphate Substances 0.000 claims description 18
- 235000019826 ammonium polyphosphate Nutrition 0.000 claims description 18
- 229920001276 ammonium polyphosphate Polymers 0.000 claims description 18
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 18
- 229920000877 Melamine resin Polymers 0.000 claims description 16
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005303 weighing Methods 0.000 claims description 14
- -1 polyethylene Polymers 0.000 claims description 13
- 239000004698 Polyethylene Substances 0.000 claims description 12
- 235000021355 Stearic acid Nutrition 0.000 claims description 12
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 12
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 claims description 12
- 239000008116 calcium stearate Substances 0.000 claims description 12
- 235000013539 calcium stearate Nutrition 0.000 claims description 12
- OEIWPNWSDYFMIL-UHFFFAOYSA-N dioctyl benzene-1,4-dicarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C=C1 OEIWPNWSDYFMIL-UHFFFAOYSA-N 0.000 claims description 12
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 12
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 12
- 229920000573 polyethylene Polymers 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 235000012424 soybean oil Nutrition 0.000 claims description 12
- 239000003549 soybean oil Substances 0.000 claims description 12
- 239000008117 stearic acid Substances 0.000 claims description 12
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000012986 modification Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 8
- 230000003179 granulation Effects 0.000 claims description 8
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical group [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 7
- 238000007599 discharging Methods 0.000 claims description 7
- 239000006084 composite stabilizer Substances 0.000 claims description 6
- 239000001993 wax Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 3
- 239000000779 smoke Substances 0.000 abstract description 9
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 231100000956 nontoxicity Toxicity 0.000 abstract description 3
- 230000001629 suppression Effects 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000004891 communication Methods 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 235000019198 oils Nutrition 0.000 description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 206010033799 Paralysis Diseases 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- GANNOFFDYMSBSZ-UHFFFAOYSA-N [AlH3].[Mg] Chemical class [AlH3].[Mg] GANNOFFDYMSBSZ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012757 flame retardant agent Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
- H01B3/44—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins
- H01B3/443—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes vinyl resins; acrylic resins from vinylhalogenides or other halogenoethylenic compounds
-
- 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
- C08K2003/322—Ammonium phosphate
- C08K2003/323—Ammonium polyphosphate
-
- 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
- C08K3/38—Boron-containing compounds
- C08K2003/387—Borates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
-
- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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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)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-fluidity flame-retardant PVC material and a preparation method thereof, wherein the high-fluidity flame-retardant PVC material comprises the following raw materials in parts by weight: PVC resin A:20-30 parts of a solvent; PVC resin B:20-30 parts of a solvent; plasticizer: 20-25 parts; flame retardant: 15-20 parts of a solvent; a stabilizer: 3-4 parts; lubricant: 0.4-0.6 part; antioxidant: 0.2-0.4 part; the preparation method comprises the steps of uniformly mixing the materials, granulating, extruding and molding, and no other solvent is required to be added. The invention does not adopt halogen flame retardant for flame retardance, so that the PVC material prepared by the invention not only has good flame retardance, but also has the advantages of environmental protection, safety, smoke suppression, no toxicity and low price; and any other solvent is not needed to be added in the preparation process, so that the preparation process is simplified, and the energy and the time are saved.
Description
Technical Field
The invention relates to the field of PVC material preparation, in particular to a high-fluidity flame-retardant PVC material and a preparation method thereof.
Background
With the rapid development of industrialization in China, the service requirements of communication systems, monitoring and control are rapidly increased, and a large number of communication cables and equipment are widely applied. Meanwhile, with frequent occurrence of various accidents and disasters, optical cables, cables and the like often play the role of a fuse, so that the fire disaster is rapidly spread, valuable electronic instruments and equipment are damaged, the normal operation of the whole line is influenced, and even the whole line is paralyzed, and the loss of the disasters is enlarged.
The halogen-containing flame retardant (especially chlorine-based flame retardant and bromine-based flame retardant) is widely used for cable sheaths and plays a good flame-retardant role, but the sheath material adopting the halogen-containing flame retardant can generate a large amount of toxic and corrosive gas and smoke in the combustion process, so that people are suffocated and poisoned, and the harm of the halogen-containing flame retardant is more serious than that of the fire per se.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a high-fluidity flame-retardant PVC material and a preparation method thereof, so that the PVC material has low smoke and low toxicity and has a better flame-retardant effect.
The purpose of the invention is realized by the following technical scheme: a high-fluidity flame-retardant PVC material comprises the following raw materials in parts by weight:
PVC resin A:20-30 parts;
PVC resin B:20-30 parts of a solvent;
plasticizer: 20-25 parts;
flame retardant: 15-20 parts of a solvent;
a stabilizer: 3-4 parts;
lubricant: 0.4 to 0.6 portion;
antioxidant: 0.2 to 0.4 portion.
Further, the flame retardant is a mixture of magnesium-aluminum hydrotalcite subjected to surface modification treatment, melamine-coated ammonium polyphosphate and zinc borate; the weight ratio of the magnesium-aluminum hydrotalcite to the melamine-coated ammonium polyphosphate to the zinc borate is 5-6. The surface modification treatment of the flame retardant comprises the following specific steps:
s1, weighing magnesium aluminum hydrotalcite, melamine coated ammonium polyphosphate and zinc borate, m Magnesium aluminum hydrotalcite ：m Melamine coated ammonium polyphosphate ：m Zinc borate ＝5:1:1；
S2, weighing a silane coupling agent and diluting the silane coupling agent by white oil, wherein the weight of the silane coupling agent is 1.0-1.2% of the sum of the weight of the magnesium-aluminum hydrotalcite, the weight of the melamine-coated ammonium polyphosphate and the weight of the zinc borate; the amount of the white oil is 10-15% of the weight of the silane coupling agent;
s3, adding the magnesium-aluminum hydrotalcite weighed in the step S1, melamine-coated ammonium polyphosphate and zinc borate into a high-speed stirrer, preheating and stirring for 3-5min at the temperature of 90-100 ℃;
and S4, adding the silane coupling agent diluted by the white oil in the step S2 into the high-speed stirrer, continuously stirring for 5-8min, and discharging for later use.
The flame retardant is a mixture of magnesium-aluminum hydrotalcite and melamine-coated ammonium polyphosphate and zinc borate, wherein the magnesium-aluminum hydrotalcite has the advantages of aluminum hydroxide and magnesium hydroxide flame retardants, the initial decomposition temperature is 200-320 ℃, and the application range is wider; the ammonium polyphosphate and the zinc borate are used as flame retardant synergist of the magnesium-aluminum hydrotalcite, the halogen-free environment-friendly flame retardant for improving the flame retardant effect of the magnesium-aluminum hydrotalcite has the advantages of environmental protection, safety, smoke suppression, no toxicity and low price, can achieve the flame retardant effect when used for flame retardance, has the characteristics of low smoke and low toxicity, and is extremely low in harm to other surrounding environments, healthy and environment-friendly.
Further, the average polymerization degree of the PVC resin A is 981-1135, and the average polymerization degree of the PVC resin B is 741-845; the PVC resin A has better mechanical property but insufficient processability; the PVC resin B has good processability but poor mechanical property, and the mechanical property and the processability are both considered by adopting a mode of mixing the PVC resin B and the PVC resin B.
Further, the plasticizer is a mixture of dioctyl terephthalate and epoxidized soybean oil, and the weight ratio of the dioctyl terephthalate to the epoxidized soybean oil is 4:1; the dioctyl terephthalate is an environment-friendly plasticizer, the plasticizing efficiency is high, and the epoxidized soybean oil has the functions of both the plasticizer and the heat-resistant stabilizer.
Further, the stabilizer is a calcium-zinc composite stabilizer; the calcium zinc stabilizer does not contain heavy metals such as lead, cadmium and the like, and is an environment-friendly stabilizer.
Further, the lubricant is a mixture of polyethylene wax, stearic acid and calcium stearate; the weight ratio of the polyethylene wax to the stearic acid to the calcium stearate is 1:1:2; the melting point of the stearic acid is 67-72 ℃, the melting point of the polyethylene wax is 100-105 ℃, the melting point of the calcium stearate is 147-149 ℃, and the lubricating requirements of the PVC material from low temperature to high temperature in the preparation and processing processes are met by adopting a mode of combining three lubricants with different low, medium and high melting points, so that the fluidity and the processing performance of the material are effectively improved.
Further, the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168; the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:2; the antioxidant 1010 belongs to hindered phenol antioxidants, and can continuously play an antioxidant role for a long time by capturing free radicals generated in the degradation process of PVC; the antioxidant 168 phosphite esters are used as auxiliary antioxidants, and the antioxidant purpose is achieved by decomposing peroxide generated by further degrading PVC, so that the heat processing stability is provided.
A preparation method of a high-fluidity flame-retardant PVC material comprises the following steps:
s1, weighing: weighing 20-30 parts of PVC resin A, 20-30 parts of PVC resin B, 20-25 parts of plasticizer, 15-20 parts of flame retardant, 3-4 parts of stabilizer, 0.4-0.6 part of lubricant and 0.2-0.4 part of antioxidant in parts by weight for later use;
s2, mixing:
s21, adding the PVC resin, the flame retardant, the stabilizer, the lubricant and the antioxidant into a high-speed mixer according to the proportion in the step S1, and mixing for 1min at the temperature of 60-70 ℃ at 600-700 r/min to obtain a first mixed material;
s22, adding a plasticizer into the first mixed material according to the proportion in the step S1 under the stirring conditions of 80-90 ℃ and 600-700 r/min; continuously stirring at the rotating speed of 1100-1300 r/min, obtaining a second mixed material when the temperature of the material reaches 105-110 ℃, and discharging for later use;
s3, extruding and granulating: and putting the second mixed material into a double-stage granulator set for extrusion granulation to obtain the high-fluidity flame-retardant PVC material.
Further, in the step S3, during extrusion granulation, the rotating speed of the double-screw extruder is 260-320 r/min, and the temperature of the body of the double-screw extruder is controlled at 130-160 ℃; the feeding speed of the single screw extruder is 35-40 r/min, and the temperature of the single screw extruder body is controlled at 120-150 ℃.
The beneficial effects of the invention are:
(1) The high-fluidity flame-retardant PVC material is prepared by taking the PVC resin, the environment-friendly plasticizer and the environment-friendly flame retardant as main raw materials, does not contain a halogen flame retardant, is low in smoke and non-toxic during combustion, and is environment-friendly.
(2) The flame retardant selected by the invention is the surface-modified magnesium-aluminum hydrotalcite, which has the advantages of aluminum hydroxide and magnesium hydroxide flame retardants, and has the initial decomposition temperature of 200-320 ℃, and wider application range; meanwhile, the ammonium polyphosphate and the zinc borate are used as the flame-retardant synergist of the magnesium-aluminum hydrotalcite, so that the flame-retardant effect of the magnesium-aluminum hydrotalcite is improved, and compared with a halogen flame retardant, the flame-retardant agent has the advantages of excellent flame-retardant effect, environmental friendliness, safety, smoke suppression, no toxicity, low price, little harm to other surrounding environments, and health and environmental protection.
(3) According to the high-fluidity flame-retardant PVC material and the preparation method thereof, raw materials do not contain any solvent, and the mixing and extrusion molding are continuously carried out, so that the production process is optimized, and the high-fluidity flame-retardant PVC material has social significance of energy conservation and environmental protection; the obtained low-smoke halogen-free flame-retardant communication cable sheath material has excellent flame retardance, processing resistance and insulating property, and the preparation method is environment-friendly, simple in process, energy-saving and time-saving.
Detailed Description
The technical solutions of the present invention are further described in detail below with reference to examples, but the scope of the present invention is not limited to the following.
Example 1
A high-fluidity flame-retardant PVC material is prepared from PVC resin A:20 parts of PVC resin B:30 parts of plasticizer: 25 parts of flame retardant: 20 parts of stabilizer: 4 parts of lubricant: 0.5 part of antioxidant: 0.3 part of a stabilizer; the flame retardant is a mixture of magnesium-aluminum hydrotalcite subjected to surface modification treatment, melamine-coated ammonium polyphosphate and zinc borate; the weight ratio of the magnesium-aluminum hydrotalcite to the melamine-coated ammonium polyphosphate to the zinc borate is 5; the average polymerization degree of the PVC resin A is 981-1135, and the average polymerization degree of the PVC resin B is 741-845; the plasticizer is a mixture of dioctyl terephthalate and epoxidized soybean oil, and the weight ratio of the dioctyl terephthalate to the epoxidized soybean oil is 4:1; the stabilizer is a calcium-zinc composite stabilizer; the lubricant is a mixture of polyethylene wax, stearic acid and calcium stearate; the weight ratio of the polyethylene wax to the stearic acid to the calcium stearate is 1:1:2; the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168; the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:2;
the preparation method comprises the following steps:
s1, weighing: weighing 20 parts of PVC resin A, 30 parts of PVC resin B, 25 parts of plasticizer, 20 parts of flame retardant, 4 parts of stabilizer, 0.5 part of lubricant and 0.3 part of antioxidant for later use;
s2, mixing:
s21, adding the PVC resin, the flame retardant, the stabilizer, the lubricant and the antioxidant into a high-speed mixer according to the proportion in the step S1, and mixing for 1min at the temperature of 60-70 ℃ at 600-700 r/min to obtain a first mixed material;
s22, adding a plasticizer into the first mixed material according to the proportion in the step S1 under the stirring condition of 80-90 ℃ and 600-700 r/min; continuously stirring at the rotating speed of 1100-1300 r/min, obtaining a second mixed material when the temperature of the material reaches 105-110 ℃, and discharging for later use;
s3, extruding and granulating: putting the second mixed material into a double-stage granulator set for extrusion granulation to obtain a high-fluidity flame-retardant PVC material; when extruding and granulating, the rotating speed of the double-screw extruder is 260-320 r/min, and the temperature of the body of the double-screw extruder is controlled at 130-160 ℃; the feeding speed of the single screw extruder is 35-40 r/min, and the temperature of the single screw extruder body is controlled at 120-150 ℃.
Example 2
A high-fluidity flame-retardant PVC material is prepared from PVC resin A:25 parts of PVC resin B:25 parts of plasticizer: 25 parts of flame retardant: 20 parts of a stabilizer: 4 parts of lubricant: 0.5 part of antioxidant: 0.3 part of a stabilizer; the flame retardant is a mixture of magnesium-aluminum hydrotalcite subjected to surface modification treatment, melamine-coated ammonium polyphosphate and zinc borate; the weight ratio of the magnesium-aluminum hydrotalcite to the melamine-coated ammonium polyphosphate to the zinc borate is (5); the average polymerization degree of the PVC resin A is 981-1135, and the average polymerization degree of the PVC resin B is 741-845; the plasticizer is a mixture of dioctyl terephthalate and epoxidized soybean oil, and the weight ratio of the dioctyl terephthalate to the epoxidized soybean oil is 4:1; the stabilizer is a calcium-zinc composite stabilizer; the lubricant is a mixture of polyethylene wax, stearic acid and calcium stearate; the weight ratio of the polyethylene wax to the stearic acid to the calcium stearate is 1:1:2; the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168; the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:2;
the preparation method comprises the following steps:
s1, weighing: weighing 25 parts of PVC resin A, 25 parts of PVC resin B, 25 parts of plasticizer, 20 parts of flame retardant, 4 parts of stabilizer, 0.5 part of lubricant and 0.3 part of antioxidant for later use;
s2, mixing:
s21, adding the PVC resin, the flame retardant, the stabilizer, the lubricant and the antioxidant into a high-speed mixer according to the proportion in the step S1, and mixing for 1min at the temperature of 60-70 ℃ at 600-700 r/min to obtain a first mixed material;
s22, adding a plasticizer into the first mixed material according to the proportion in the step S1 under the stirring conditions of 80-90 ℃ and 600-700 r/min; continuously stirring at the rotating speed of 1100-1300 r/min, obtaining a second mixed material when the temperature of the material reaches 105-110 ℃, and discharging for later use;
s3, extruding and granulating: putting the second mixed material into a double-stage granulator set for extrusion granulation to obtain a high-fluidity flame-retardant PVC material; when extruding and granulating, the rotating speed of the double-screw extruder is 260-320 r/min, and the temperature of the body of the double-screw extruder is controlled at 130-160 ℃; the feeding speed of the single screw extruder is 35-40 r/min, and the temperature of the single screw extruder body is controlled at 120-150 ℃.
Example 3
A high-fluidity flame-retardant PVC material is prepared from PVC resin A:30 parts of PVC resin B:20 parts of plasticizer: 25 parts of flame retardant: 20 parts of a stabilizer: 4 parts of lubricant: 0.5 part of antioxidant: 0.3 part of a stabilizer; the flame retardant is a mixture of magnesium-aluminum hydrotalcite subjected to surface modification treatment, melamine-coated ammonium polyphosphate and zinc borate; the weight ratio of the magnesium-aluminum hydrotalcite to the melamine-coated ammonium polyphosphate to the zinc borate is 5; the average polymerization degree of the PVC resin A is 981-1135, and the average polymerization degree of the PVC resin B is 741-845; the plasticizer is a mixture of dioctyl terephthalate and epoxidized soybean oil, and the weight ratio of the dioctyl terephthalate to the epoxidized soybean oil is 4:1; the stabilizer is a calcium-zinc composite stabilizer; the lubricant is a mixture of polyethylene wax, stearic acid and calcium stearate; the weight ratio of the polyethylene wax to the stearic acid to the calcium stearate is 1:1:2; the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168; the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:2;
the preparation method comprises the following steps:
s1, weighing: weighing 30 parts of PVC resin A, 20 parts of PVC resin B, 25 parts of plasticizer, 20 parts of flame retardant, 4 parts of stabilizer, 0.5 part of lubricant and 0.3 part of antioxidant for later use;
s2, mixing:
s21, adding the PVC resin, the flame retardant, the stabilizer, the lubricant and the antioxidant into a high-speed mixer according to the proportion in the step S1, and mixing for 1min at the temperature of 60-70 ℃ at 600-700 r/min to obtain a first mixed material;
s22, adding a plasticizer into the first mixed material according to the proportion in the step S1 under the stirring condition of 80-90 ℃ and 600-700 r/min; continuously stirring at the rotating speed of 1100-1300 r/min, obtaining a second mixed material when the temperature of the materials reaches 105-110 ℃, and discharging for later use;
s3, extruding and granulating: putting the second mixed material into a double-stage granulator set for extrusion granulation to obtain a high-fluidity flame-retardant PVC material; when extruding and granulating, the rotating speed of the double-screw extruder is 260-320 r/min, and the temperature of the body of the double-screw extruder is controlled at 130-160 ℃; the feeding speed of the single screw extruder is 35-40 r/min, and the temperature of the single screw extruder body is controlled at 120-150 ℃.
Example 4
A high-fluidity flame-retardant PVC material is prepared from PVC resin A:30 parts of PVC resin B:20 parts of plasticizer: 22 parts of flame retardant: 15 parts of stabilizer: 4 parts of lubricant: 0.5 part of antioxidant: 0.3 part of a stabilizer; the flame retardant is a mixture of magnesium-aluminum hydrotalcite subjected to surface modification treatment, melamine-coated ammonium polyphosphate and zinc borate; the weight ratio of the magnesium-aluminum hydrotalcite to the melamine-coated ammonium polyphosphate to the zinc borate is 5; the average polymerization degree of the PVC resin A is 981-1135, and the average polymerization degree of the PVC resin B is 741-845; the plasticizer is a mixture of dioctyl terephthalate and epoxidized soybean oil, and the weight ratio of the dioctyl terephthalate to the epoxidized soybean oil is 4:1; the stabilizer is a calcium-zinc composite stabilizer; the lubricant is a mixture of polyethylene wax, stearic acid and calcium stearate; the weight ratio of the polyethylene wax to the stearic acid to the calcium stearate is 1:1:2; the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168; the weight ratio of the antioxidant 1010 to the antioxidant 168 is 1:2;
the preparation method comprises the following steps:
s1, weighing: weighing 30 parts of PVC resin A, 20 parts of PVC resin B, 22 parts of plasticizer, 15 parts of flame retardant, 4 parts of stabilizer, 0.5 part of lubricant and 0.3 part of antioxidant for later use;
s2, mixing:
s21, adding the PVC resin, the flame retardant, the stabilizer, the lubricant and the antioxidant into a high-speed mixer according to the proportion in the step S1, and mixing for 1min at the temperature of 60-70 ℃ at 600-700 r/min to obtain a first mixed material;
s22, adding a plasticizer into the first mixed material according to the proportion in the step S1 under the stirring conditions of 80-90 ℃ and 600-700 r/min; continuously stirring at the rotating speed of 1100-1300 r/min, obtaining a second mixed material when the temperature of the material reaches 105-110 ℃, and discharging for later use;
s3, extruding and granulating: putting the second mixed material into a double-stage granulator set for extrusion granulation to obtain a high-fluidity flame-retardant PVC material; when extruding and granulating, the rotating speed of the double-screw extruder is 260-320 r/min, and the temperature of the body of the double-screw extruder is controlled at 130-160 ℃; the feeding speed of the single screw extruder is 35-40 r/min, and the temperature of the single screw extruder body is controlled at 120-150 ℃.
The materials prepared in examples 1 to 4 were tested for their properties, and the results are shown in Table 1.
Table 1: high-fluidity flame-retardant PVC material performance test result
As can be seen from the table 1, the oxygen index of the PVC material prepared by the invention is higher than 34%, and the PVC material has excellent flame retardant property; and the smoke generated during combustion is low in amount, low in toxicity, basically harmless to the environment and excellent in mechanical property.
The foregoing is illustrative of the preferred embodiments of this invention, and it is to be understood that the invention is not limited to the precise form disclosed herein and that various other combinations, modifications, and environments may be resorted to, falling within the scope of the concept as disclosed herein, either as described above or as apparent to those skilled in the relevant art. And that modifications and variations may be effected by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (9)
1. The high-fluidity flame-retardant PVC material is characterized by comprising the following raw materials in parts by weight:
PVC resin A:20-30 parts of a solvent;
PVC resin B:20-30 parts of a solvent;
plasticizer: 20-25 parts;
flame retardant: 15-20 parts of a solvent;
a stabilizer: 3-4 parts;
lubricant: 0.4 to 0.6 portion;
antioxidant: 0.2 to 0.4 portion.
2. A high flow flame retardant PVC material in accordance with claim 1, characterized in that: the flame retardant is a mixture of magnesium-aluminum hydrotalcite subjected to surface modification treatment, melamine-coated ammonium polyphosphate and zinc borate.
3. A high flow flame retardant PVC material in accordance with claim 1, characterized by: the average polymerization degree of the PVC resin A is 981-1135, and the average polymerization degree of the PVC resin B is 741-845.
4. A high flow flame retardant PVC material in accordance with claim 1, characterized by: the plasticizer is a mixture of dioctyl terephthalate and epoxidized soybean oil.
5. A high flow flame retardant PVC material in accordance with claim 1, characterized by: the stabilizer is a calcium-zinc composite stabilizer.
6. A high flow flame retardant PVC material in accordance with claim 1, characterized by: the lubricant is a mixture of polyethylene wax, stearic acid and calcium stearate.
7. A high flow flame retardant PVC material in accordance with claim 1, characterized by: the antioxidant is a mixture of an antioxidant 1010 and an antioxidant 168.
8. The preparation method of the high-fluidity flame-retardant PVC material is characterized by comprising the following steps of:
s1, weighing: weighing 20-30 parts of PVC resin A, 20-30 parts of PVC resin B, 20-25 parts of plasticizer, 15-20 parts of flame retardant, 3-4 parts of stabilizer, 0.4-0.6 part of lubricant and 0.2-0.4 part of antioxidant for later use;
s2, mixing:
s21, adding the PVC resin, the flame retardant, the stabilizer, the lubricant and the antioxidant into a high-speed mixer according to the proportion in the step S1, and mixing for 1min at the temperature of 60-70 ℃ at 600-700 r/min to obtain a first mixed material;
s22, adding a plasticizer into the first mixed material according to the proportion in the step S1 under the stirring conditions of 80-90 ℃ and 600-700 r/min; continuously stirring at the rotating speed of 1100-1300 r/min, obtaining a second mixed material when the temperature of the material reaches 105-110 ℃, and discharging for later use;
s3, extruding and granulating: and putting the second mixed material into a double-stage granulator set for extrusion granulation to obtain the high-fluidity flame-retardant PVC material.
9. The method for preparing high-fluidity flame-retardant PVC material according to claim 8, characterized in that: in the step S3, during extrusion granulation, the rotating speed of the double-screw extruder is 260-320 r/min, and the temperature of the body of the double-screw extruder is controlled at 130-160 ℃; the feeding speed of the single screw extruder is 35-40 r/min, and the temperature of the single screw extruder body is controlled at 120-150 ℃.
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