CN114656729A - High-flame-retardant low-temperature-resistant polyvinyl chloride composition and preparation method and application thereof - Google Patents
High-flame-retardant low-temperature-resistant polyvinyl chloride composition and preparation method and application thereof Download PDFInfo
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- CN114656729A CN114656729A CN202210271345.5A CN202210271345A CN114656729A CN 114656729 A CN114656729 A CN 114656729A CN 202210271345 A CN202210271345 A CN 202210271345A CN 114656729 A CN114656729 A CN 114656729A
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- polyvinyl chloride
- flame
- chloride composition
- temperature
- flame retardant
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- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 79
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 79
- 239000003063 flame retardant Substances 0.000 title claims abstract description 76
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 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 claims abstract description 57
- 239000004014 plasticizer Substances 0.000 claims abstract description 32
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 20
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 20
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 20
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 150000003751 zinc Chemical class 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 18
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 14
- 239000012745 toughening agent Substances 0.000 claims abstract description 14
- 239000002245 particle Substances 0.000 claims description 18
- -1 zinc aluminate Chemical class 0.000 claims description 16
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- 238000006116 polymerization reaction Methods 0.000 claims description 7
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 6
- 239000000347 magnesium hydroxide Substances 0.000 claims description 6
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 6
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims description 5
- WGEATSXPYVGFCC-UHFFFAOYSA-N zinc ferrite Chemical compound O=[Zn].O=[Fe]O[Fe]=O WGEATSXPYVGFCC-UHFFFAOYSA-N 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 229920001971 elastomer Polymers 0.000 claims description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- MTYUOIVEVPTXFX-UHFFFAOYSA-N bis(2-propylheptyl) benzene-1,2-dicarboxylate Chemical compound CCCCCC(CCC)COC(=O)C1=CC=CC=C1C(=O)OCC(CCC)CCCCC MTYUOIVEVPTXFX-UHFFFAOYSA-N 0.000 claims description 3
- ZFMQKOWCDKKBIF-UHFFFAOYSA-N bis(3,5-difluorophenyl)phosphane Chemical compound FC1=CC(F)=CC(PC=2C=C(F)C=C(F)C=2)=C1 ZFMQKOWCDKKBIF-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 3
- 239000000806 elastomer Substances 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- 239000004709 Chlorinated polyethylene Substances 0.000 claims description 2
- PYGXAGIECVVIOZ-UHFFFAOYSA-N Dibutyl decanedioate Chemical compound CCCCOC(=O)CCCCCCCCC(=O)OCCCC PYGXAGIECVVIOZ-UHFFFAOYSA-N 0.000 claims description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims description 2
- SHLNMHIRQGRGOL-UHFFFAOYSA-N barium zinc Chemical compound [Zn].[Ba] SHLNMHIRQGRGOL-UHFFFAOYSA-N 0.000 claims description 2
- UUEDINPOVKWVAZ-UHFFFAOYSA-N bis(2-ethylhexyl) 3,4,5,6-tetrabromobenzene-1,2-dicarboxylate Chemical compound CCCCC(CC)COC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(=O)OCC(CC)CCCC UUEDINPOVKWVAZ-UHFFFAOYSA-N 0.000 claims description 2
- QQVHEQUEHCEAKS-UHFFFAOYSA-N diundecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCC QQVHEQUEHCEAKS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012188 paraffin wax Substances 0.000 claims description 2
- 229920001897 terpolymer Polymers 0.000 claims description 2
- JNXDCMUUZNIWPQ-UHFFFAOYSA-N trioctyl benzene-1,2,4-tricarboxylate Chemical compound CCCCCCCCOC(=O)C1=CC=C(C(=O)OCCCCCCCC)C(C(=O)OCCCCCCCC)=C1 JNXDCMUUZNIWPQ-UHFFFAOYSA-N 0.000 claims description 2
- ASLWPAWFJZFCKF-UHFFFAOYSA-N tris(1,3-dichloropropan-2-yl) phosphate Chemical compound ClCC(CCl)OP(=O)(OC(CCl)CCl)OC(CCl)CCl ASLWPAWFJZFCKF-UHFFFAOYSA-N 0.000 claims description 2
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 6
- 239000006057 Non-nutritive feed additive Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 239000003098 androgen Substances 0.000 description 3
- 229940030486 androgens Drugs 0.000 description 3
- 229910052787 antimony Inorganic materials 0.000 description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- VJHINFRRDQUWOJ-UHFFFAOYSA-N dioctyl sebacate Chemical compound CCCCC(CC)COC(=O)CCCCCCCCC(=O)OCC(CC)CCCC VJHINFRRDQUWOJ-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000013873 oxidized polyethylene wax Nutrition 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- XIRDTMSOGDWMOX-UHFFFAOYSA-N 3,4,5,6-tetrabromophthalic acid Chemical compound OC(=O)C1=C(Br)C(Br)=C(Br)C(Br)=C1C(O)=O XIRDTMSOGDWMOX-UHFFFAOYSA-N 0.000 description 1
- AJZDHLHTTJRNQJ-UHFFFAOYSA-N 3-[4-(aminomethyl)-6-(trifluoromethyl)pyridin-2-yl]oxy-N-[2-(tetrazol-1-yl)ethyl]benzamide Chemical compound N1(N=NN=C1)CCNC(C1=CC(=CC=C1)OC1=NC(=CC(=C1)CN)C(F)(F)F)=O AJZDHLHTTJRNQJ-UHFFFAOYSA-N 0.000 description 1
- 101500000959 Bacillus anthracis Protective antigen PA-20 Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BJAJDJDODCWPNS-UHFFFAOYSA-N dotp Chemical compound O=C1N2CCOC2=NC2=C1SC=C2 BJAJDJDODCWPNS-UHFFFAOYSA-N 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 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 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
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2227—Oxides; Hydroxides of metals of aluminium
-
- 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
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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 relates to a high flame-retardant low-temperature-resistant polyvinyl chloride composition, and a preparation method and application thereof. The high-flame-retardant low-temperature-resistant polyvinyl chloride composition comprises polyvinyl chloride resin, polyvinyl chloride grafted thermoplastic polyurethane resin, a main plasticizer, a cold-resistant auxiliary plasticizer, a toughening agent, a plasticizing flame retardant, metal hydroxide, metal oxide, nano zinc salt, a stabilizer and the like. The polyvinyl chloride resin and the polyvinyl chloride grafted thermoplastic polyurethane resin are used as base materials, and the high flame retardance and low temperature resistance are realized by utilizing the synergy of the main plasticizer, the cold-resistant auxiliary plasticizer, the toughening agent, the plasticizing flame retardant, the metal hydroxide, the metal oxide, the nano zinc salt and other multiple components, so that the obtained high flame retardance and low temperature resistance polyvinyl chloride composition has excellent oxygen index and low temperature impact resistance.
Description
Technical Field
The invention belongs to the technical field of general plastics, and particularly relates to a high-flame-retardant low-temperature-resistant polyvinyl chloride composition, and a preparation method and application thereof.
Background
The flame-retardant plasticized soft polyvinyl chloride material has excellent processability and flame retardance, has higher cost performance, and can be widely applied to electronics, particularly connectors, wires and cables and the like.
The flame-retardant plasticized soft polyvinyl chloride material prepared under the existing technical conditions has a great defect that: because the physical properties of the soft polyvinyl chloride are greatly influenced along with the external temperature, when a large amount of flame retardant is added to obtain higher flame retardance in the later period, the two factors are superposed to cause that the soft polyvinyl chloride, especially the high-flame-retardant soft polyvinyl chloride, is resistant to low temperature difference, so that the application of the material is partially limited and is extruded by market space from materials such as TPU, TPE and the like.
The existing patent at present discloses a cold-resistant flame-retardant PVC cable sheath material, wherein the cold resistance is improved by compounding a cold-resistant plasticizer DOS plasticizer, so that embrittlement at low temperature can be prevented; the flame retardant property is improved by selecting a specific flame retardant system, and the dosage of the flame retardant is regulated and controlled to avoid great negative effects on the low-temperature impact property. However, the oxygen index of the PVC material obtained by the scheme is about 31 percent, and the PVC material still has a larger lifting space.
Therefore, the development of the PVC material with better flame retardant and low temperature resistance has important research significance and application value.
Disclosure of Invention
The invention aims to overcome the defects or shortcomings of the prior art and provide a high-flame-retardant low-temperature-resistant polyvinyl chloride composition. The polyvinyl chloride resin and the polyvinyl chloride grafted thermoplastic polyurethane resin are used as base materials, and the high flame retardance and low temperature resistance are realized by utilizing the synergy of the main plasticizer, the cold-resistant auxiliary plasticizer, the toughening agent, the plasticizing flame retardant, the metal hydroxide, the metal oxide, the nano zinc salt and other multiple components, so that the obtained high flame retardance and low temperature resistance polyvinyl chloride composition has excellent oxygen index and low temperature impact resistance.
The invention also aims to provide a preparation method of the high-flame-retardant low-temperature-resistant polyvinyl chloride composition.
The invention also aims to provide application of the high-flame-retardant low-temperature-resistant polyvinyl chloride composition in preparing electronic and electrical products.
In order to achieve the purpose, the invention adopts the following technical scheme:
a high flame-retardant low-temperature-resistant polyvinyl chloride composition comprises the following components in parts by weight:
65-85 parts of polyvinyl chloride resin,
15-35 parts of polyvinyl chloride grafted thermoplastic polyurethane resin,
70-90 parts of a primary plasticizer,
5-15 parts of cold-resistant auxiliary plasticizer,
10-25 parts of a toughening agent,
4-12 parts of a plasticizing flame retardant,
6 to 14 parts of a metal hydroxide,
2 to 10 parts of a metal oxide,
1-7 parts of nano zinc salt and 2-8 parts of stabilizer; the nano zinc salt is one or more of nano zinc ferrite or nano zinc aluminate.
The invention realizes high flame retardance and low temperature resistance through the cooperation of multiple components. Specifically, the method comprises the following steps:
(1) the polyvinyl chloride resin and the polyvinyl chloride grafted thermoplastic polyurethane resin are compounded to serve as the base resin, so that the low-temperature resistance can be improved, the using amount of the plasticizer is reduced, and the negative influence on the flame retardant property is avoided while the absorption of the plasticizer is not influenced;
(2) the main plasticizer and the cold-resistant auxiliary plasticizer are compounded, and the introduction of a proper amount of cold-resistant plasticizer in the system can improve the low-temperature resistance of the material to a certain extent on the premise of ensuring no precipitation.
(3) Due to the introduction of the toughening agent, the development of silver streaks of the material can be effectively prevented and the low-temperature resistance performance can be improved under the condition that the material is impacted at low temperature because of the rubber component in the toughening agent.
(4) The plasticized flame retardant, the metal hydroxide, the metal oxide and the nano zinc salt are compounded to be used as a flame retardant compound, the plasticized flame retardant is liquid, and compared with an inorganic micron-level conventional non-plasticized flame retardant, the plasticized flame retardant can realize plasticization and has certain flame retardance, and meanwhile, the deterioration of the low-temperature performance of the polyvinyl chloride composition is avoided to a greater extent; the filled flame-retardant substances such as metal hydroxide are decomposed and desorbed when the filled flame-retardant substances are ignited and heated, so that the decomposition of PVC is delayed, but a large amount of the filled flame-retardant substances are generally added to effectively decompose and absorb heat and delay the decomposition of PVC, and meanwhile, the filled flame-retardant substances also have great negative effects on the low-temperature performance of the polyvinyl chloride composition; the metal oxide is used as a synergistic flame-retardant system, so that the flame-retardant effect is further improved; the introduction of the nano zinc salt with specific particle size can effectively improve the thermal decomposition and carbon formation property when the material is fired and heated by a small amount of addition, and can greatly reduce the usage amount of metal hydroxide and metal oxide. By regulating and controlling the proportion of each component, high flame retardant effect is obtained under the condition of less addition of metal oxide and metal hydroxide, and meanwhile, the negative influence on the low temperature resistance of the polyvinyl chloride composition is small.
The components are cooperatively matched, so that the high flame retardance and the better low temperature resistance are realized, and the obtained high flame retardance low temperature resistant polyvinyl chloride composition has excellent oxygen index and low temperature impact resistance.
Preferably, the polyvinyl chloride resin has an average polymerization degree of 1300 to 2000.
The average polymerization degree of the polyvinyl chloride resin is measured by GB/T5761-2006 suspension method general polyvinyl chloride resin appendix A.
Preferably, the grafting ratio of the polyvinyl chloride grafted thermoplastic polyurethane resin is 5-20 mol%.
The grafting rate of the polyvinyl chloride grafted thermoplastic polyurethane resin is determined by an infrared standard curve method
Both primary and cold-resistant secondary plasticizers conventional in the art may be used in the present invention.
Preferably, the primary plasticizer is one or more of dioctyl terephthalate, di (2-propylheptyl) phthalate, trioctyl trimellitate or diundecyl phthalate.
Preferably, the cold-resistant auxiliary plasticizer is one or more of dioctyl sebacate, dioctyl adipate or di-n-butyl sebacate.
Preferably, the toughening agent is one or more of vinyl elastomer, chlorinated polyethylene, terpolymer of methyl methacrylate, butadiene and styrene, or acrylate.
Preferably, the plasticizing type flame retardant is one or more of isopropylated triphenyl phosphate, tetrabromophthalic acid bis (2-ethylhexyl) ester, chlorinated paraffin or tris (1, 3-dichloroisopropyl) phosphate.
Preferably, the metal hydroxide is one or both of magnesium hydroxide and aluminum hydroxide. Further preferred is magnesium hydroxide.
Preferably, the average particle size of the metal hydroxide is 2 to 6 μm.
Preferably, the metal oxide is one or more of antimony trioxide, tin dioxide or magnesium oxide. Further preferred is an antimony trioxide, which is,
preferably, the average particle diameter of the metal oxide is 0.5 to 2 μm
Preferably, the stabilizer is one or more of a calcium zinc stabilizer, an organic tin stabilizer or a barium zinc stabilizer.
Other processing aids conventional in the art may also be used in the present invention.
Preferably, the other processing aids are one or more of acrylates or oxidized polyethylene waxes.
More preferably, the weight part of the acrylate is 1-2 parts.
More preferably, the weight part of the oxidized polyethylene waxes is 0.5-2 parts.
The preparation method of the high-flame-retardant low-temperature-resistant polyvinyl chloride composition comprises the following steps: mixing the components (polyvinyl chloride resin, polyvinyl chloride grafted thermoplastic polyurethane resin, main plasticizer, cold-resistant auxiliary plasticizer, toughening agent, plasticized flame retardant, metal hydroxide, metal oxide, nano zinc salt, stabilizer and other processing aids (if any)), plasticizing, extruding and granulating to obtain the high-flame-retardant low-temperature-resistant polyvinyl chloride composition.
Preferably, the preparation method of the high flame retardant low temperature resistant polyvinyl chloride composition comprises the following steps: mixing polyvinyl chloride resin, polyvinyl chloride grafted thermoplastic polyurethane resin and a stabilizer in a high-speed mixer, then adding a main plasticizer and a cold-resistant auxiliary plasticizer, mixing to 85-135 ℃, adding a toughening agent, a plasticizing flame retardant, a metal hydroxide, a metal oxide, a nano zinc salt and other additives (if any), and mixing to 90-140 ℃ to obtain a premix; adding the premix into a double-screw extruder for mixing, plasticizing, extruding and vacuum granulating to obtain the high-flame-retardant low-temperature-resistant polyvinyl chloride composition; the temperature of each zone of the screw of the double-screw extruder is 100-120 ℃.
The application of the high flame-retardant low-temperature-resistant polyvinyl chloride composition in the preparation of electronic and electrical products (wires, cables and the like) is also within the protection scope of the invention.
Compared with the prior art, the invention has the following beneficial effects:
the polyvinyl chloride resin and the polyvinyl chloride grafted thermoplastic polyurethane resin are used as base materials, and the high flame retardance and low temperature resistance are realized by utilizing the synergy of the main plasticizer, the cold-resistant auxiliary plasticizer, the toughening agent, the plasticizing flame retardant, the metal hydroxide, the metal oxide, the nano zinc salt and other multiple components, so that the obtained high flame retardance and low temperature resistance polyvinyl chloride composition has excellent oxygen index and low temperature impact resistance.
Detailed Description
The invention is further illustrated by the following examples. These examples are intended to illustrate the invention and are not intended to limit the scope of the invention. Experimental procedures without specific conditions noted in the examples below, generally according to conditions conventional in the art or as suggested by the manufacturer; the raw materials, reagents and the like used are, unless otherwise specified, those commercially available from the conventional markets and the like. Any insubstantial changes and substitutions made by those skilled in the art based on the present invention are intended to be covered by the claims.
Some of the reagents selected in the examples and comparative examples of the present invention are described below:
polyvinyl chloride resin 1: stage plastic, PVCS80, degree of polymerization 1800;
polyvinyl chloride resin 2: plastic table, PVCS70, degree of polymerization 1300;
polyvinyl chloride resin 3: stage plastic, PVCS85, degree of polymerization 2000;
polyvinyl chloride resin 4: stage plastic, PVCS65, polymerization degree 1000;
polyvinyl chloride graft thermoplastic polyurethane resin 1: plastic, PVCC-1800, grafting rate 5 mol%;
polyvinyl chloride graft thermoplastic polyurethane resin 2: plastic, PVCC-1000, grafting rate 20 mol%;
primary plasticizer 1: dioctyl terephthalate and DOTP are combined;
and (3) a primary plasticizer 2: di (2-propylheptyl) phthalate, linked;
cold-resistant auxiliary plasticizer 1: dioctyl sebacate, DOS, combined;
cold-resistant auxiliary plasticizer 2: dioctyl adipate, DOA;
toughening agent 1: vinyl elastomer, HP441, dupont;
a toughening agent 2: acrylates, B564, brillouin;
the flame retardant compound 1-15 is prepared by self and is prepared by compounding a plurality of components, the formula is shown in table 1, and the preparation process is as follows: weighing the components according to the proportion, and uniformly mixing to obtain the composition.
TABLE 1 flame retardant compositions 1-15
Plasticized flame retardant 1: bis (2-ethylhexyl) tetrabromophthalate, KFFR45, edentad;
plasticized flame retardant 2: isopropylated triphenyl phosphate, KFFR564, edam;
non-plasticized flame retardant: zinc borate, KFFRZ, Yishitong;
metal hydroxide 1: magnesium hydroxide, KFFRM1, androgens, average particle size 2 μm;
metal hydroxide 2: magnesium hydroxide, KFFRM2, androgens, with an average particle size of 6 μm;
metal hydroxide 3: magnesium hydroxide, KFFRM3, androgens, with an average particle size of 10 μm;
metal hydroxide 4: aluminum hydroxide, KFFRA1, star, average particle size 4 μm;
metal oxide 1: antimony trioxide, KFFRS1, antimony of the south of the lake industry, with an average particle size of 0.5 μm;
metal oxide 2: antimony trioxide, KFFRS2, antimony of the south of the lake industry, with an average particle size of 2 μm;
metal oxide 3: antimony trioxide, KFFRS3, antimony of the south of the lake industry, with an average particle size of 5 μm;
metal oxide 4: magnesium oxide, KFFRS4, erda, average particle size 1 μm;
nano zinc salt 1: nano zinc ferrite, KFFRN1, Edandard, the average grain diameter is 15 nm;
nano zinc salt 2: nano zinc ferrite, KFFRN2, Edandard, and the average grain diameter is 10 nm;
nano zinc salt 3: nano zinc ferrite, KFFRN3, Edandard, and the average grain diameter is 20 nm;
nano zinc salt 4: nano zinc aluminate, KFFRM1, Edandard, with an average particle size of 15 nm;
and (3) nano zinc salt 5: nano zinc aluminate, KFFRM1, Edandard, with an average particle size of 30 nm;
a stabilizer: RUP-108, Adecaceae;
other processing aids: acrylates, PA20, commercially available.
It is to be understood that, unless otherwise specified, certain components (e.g., other processing aids) selected in the examples and comparative examples are the same commercially available products.
The polyvinyl chloride composition in the embodiment and the comparative example is prepared by the following processes:
(1) weighing the components according to the formula content, firstly adding polyvinyl chloride resin, polyvinyl chloride grafted thermoplastic polyurethane resin and a stabilizer into a high-speed mixer, starting a high-speed mixer, then adding a main plasticizer and a cold-resistant auxiliary plasticizer, mixing to 100 ℃, adding a toughening agent, a flame retardant compound and other additives (if any), and mixing at high speed to 130 ℃ to obtain a mixed semi-finished product material;
(2) plasticizing and mixing the mixed semi-finished product material by an extruder, wherein the temperature of each zone is set as follows in sequence: the temperature of the first zone is 100 ℃, the temperature of the second zone is 110 ℃, the temperature of the third zone is 110 ℃, the temperature of the fourth zone is 115 ℃, the temperature of the fifth zone is 120 ℃, the temperature of the sixth zone is 120 ℃, the temperature of the seventh zone is 110 ℃, the temperature of the eighth zone is 110 ℃, and the temperature of the ninth zone is 110 ℃; the rotating speed of the screw is 400 r/min, and the product is obtained after granulation and packaging.
The polyvinyl chloride compositions obtained in the respective examples and comparative examples were subjected to the following tests.
(1) The low temperature resistance evaluation method comprises the following steps: and (3) measuring the brittle temperature by adopting a GB/T5470-2008 plastic impact method.
(2) The flame retardant test evaluation method comprises the following steps: GB-T2406 + 1993 is adopted; test method of Plastic Combustion Properties determination by oxygen index method.
Examples 1 to 19
This example provides a series of highly flame retardant and low temperature resistant polyvinyl chloride compositions, wherein the weight parts of the components in the formulation and the performance test results are shown in tables 2 and 3.
TABLE 2 formulations (parts) and Performance test results of examples 1-12
TABLE 3 formulations (parts) and Performance test results for examples 13-19
Comparative examples 1 to 6
This comparative example provides a series of polyvinyl chloride compositions having the formulation with the parts by weight of the components and the performance test results shown in table 4.
TABLE 4 formulations (parts) and performance test results for comparative examples 1-6
The test results show that the high-flame-retardant low-temperature-resistant polyvinyl chloride composition provided by the embodiments 1 to 19 has excellent flame retardant performance and low-temperature resistance, the oxygen index is more than 40, and the brittle temperature is below minus 45 ℃; with the best performance of example 1.
The nano zinc salt in the flame retardant composite of comparative example 1 has a large particle size and cannot sufficiently exert the efficacy of the nano flame retardant. The flame retardant compound of comparative example 2 is a non-plasticized flame retardant, and the addition of micron-sized inorganic flame retardant particles has a limited improvement in flame retardancy and may deteriorate low temperature resistance. The flame retardant composite of comparative example 3 has no metal hydroxide added, and has satisfactory low-temperature resistance, but has poor overall flame retardancy. The flame retardant compound of comparative example 4 has no metal oxide added, has good low temperature resistance, but lacks flame retardant synergy, and has poor flame retardant performance. The flame retardant compound of comparative example 5 has no nano zinc salt, has no high-efficiency flame retardance of a nano flame retardant, and has flame retardant performance inferior to that of the examples. Comparative example 6 has no polyvinyl chloride grafted thermoplastic polyurethane resin, has less low temperature resistance and has good flame retardancy.
It will be appreciated by those of ordinary skill in the art that the examples provided herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited examples and embodiments. Those skilled in the art can make various other specific changes and combinations based on the teachings of the present invention without departing from the spirit of the invention, and these changes and combinations are within the scope of the invention.
Claims (10)
1. The high-flame-retardant low-temperature-resistant polyvinyl chloride composition is characterized by comprising the following components in parts by weight:
the nano zinc salt is one or more of nano zinc ferrite or nano zinc aluminate; the average particle size of the nano zinc salt is 10-20 nm.
2. The highly flame-retardant low-temperature-resistant polyvinyl chloride composition according to claim 1, wherein the polyvinyl chloride resin has an average degree of polymerization of 1300 to 2000; the grafting amount of polyurethane in the polyvinyl chloride grafted thermoplastic polyurethane resin is 5-20 mol%.
3. The highly flame retardant low temperature resistant polyvinyl chloride composition according to claim 1 wherein said primary plasticizer is one or more of dioctyl terephthalate, di (2-propylheptyl) phthalate, trioctyl trimellitate or diundecyl phthalate; the cold-resistant auxiliary plasticizer is one or more of dioctyl sebacate, dioctyl adipate or di-n-butyl sebacate.
4. The composition of claim 1, wherein the toughening agent is one or more of vinyl elastomer, chlorinated polyethylene, terpolymer of methyl methacrylate, butadiene and styrene, or acrylate.
5. The high flame retardant low temperature resistant polyvinyl chloride composition according to claim 1, wherein the plasticized flame retardant is one or more of isopropylated triphenyl phosphate, bis (2-ethylhexyl) tetrabromophthalate, chlorinated paraffin or tris (1, 3-dichloroisopropyl) phosphate.
6. The highly flame retardant low temperature resistant polyvinyl chloride composition as claimed in claim 1, wherein the metal hydroxide is one or both of magnesium hydroxide and aluminum hydroxide; the average particle diameter of the metal hydroxide is 2-6 μm.
7. The highly flame-retardant low-temperature-resistant polyvinyl chloride composition as claimed in claim 1, wherein the metal oxide is one or more of antimony trioxide, tin dioxide or magnesium oxide; the average particle diameter of the metal oxide is 0.5 to 2 μm.
8. The high flame retardant low temperature resistant polyvinyl chloride composition according to claim 1, wherein the stabilizer is one or more of calcium zinc stabilizer, organic tin stabilizer or barium zinc stabilizer.
9. The preparation method of the high flame retardant and low temperature resistant polyvinyl chloride composition as claimed in any one of claims 1 to 8, comprising the steps of: and mixing, plasticizing, extruding and granulating the components to obtain the high-flame-retardant low-temperature-resistant polyvinyl chloride composition.
10. Use of the highly flame-retardant low-temperature-resistant polyvinyl chloride composition according to any one of claims 1 to 8 in the preparation of electronic and electrical products.
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