CN103224681B - Silicane self-crosslinked halogen-free flame retardant polyolefin foamed composite and preparation method thereof - Google Patents
Silicane self-crosslinked halogen-free flame retardant polyolefin foamed composite and preparation method thereof Download PDFInfo
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- CN103224681B CN103224681B CN201310173086.3A CN201310173086A CN103224681B CN 103224681 B CN103224681 B CN 103224681B CN 201310173086 A CN201310173086 A CN 201310173086A CN 103224681 B CN103224681 B CN 103224681B
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- flame retardant
- component
- halogen
- silane
- retardant
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 87
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 title abstract description 7
- 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 70
- 229910000077 silane Inorganic materials 0.000 claims abstract description 41
- 238000004132 cross linking Methods 0.000 claims abstract description 37
- -1 polyethylene Polymers 0.000 claims abstract description 31
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 27
- 239000004698 Polyethylene Substances 0.000 claims abstract description 27
- 229920000573 polyethylene Polymers 0.000 claims abstract description 27
- 229920001684 low density polyethylene Polymers 0.000 claims abstract description 21
- 239000004702 low-density polyethylene Substances 0.000 claims abstract description 21
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 11
- 239000003999 initiator Substances 0.000 claims abstract description 10
- 239000000314 lubricant Substances 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 5
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000006260 foam Substances 0.000 claims description 31
- 239000003112 inhibitor Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 238000006555 catalytic reaction Methods 0.000 claims description 22
- 238000002844 melting Methods 0.000 claims description 22
- 230000008018 melting Effects 0.000 claims description 22
- 239000007822 coupling agent Substances 0.000 claims description 18
- 230000004048 modification Effects 0.000 claims description 17
- 238000012986 modification Methods 0.000 claims description 17
- 239000002994 raw material Substances 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 230000001476 alcoholic effect Effects 0.000 claims description 14
- 239000006096 absorbing agent Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 10
- 239000004971 Cross linker Substances 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 9
- 239000010703 silicon Substances 0.000 claims description 9
- 238000013019 agitation Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 238000007493 shaping process Methods 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 6
- OGBUMNBNEWYMNJ-UHFFFAOYSA-N batilol Chemical class CCCCCCCCCCCCCCCCCCOCC(O)CO OGBUMNBNEWYMNJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007906 compression Methods 0.000 claims description 6
- 230000006835 compression Effects 0.000 claims description 6
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 6
- 238000005469 granulation Methods 0.000 claims description 6
- 230000003179 granulation Effects 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000004811 fluoropolymer Substances 0.000 claims description 4
- 229920002313 fluoropolymer Polymers 0.000 claims description 4
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 4
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 4
- 239000000347 magnesium hydroxide Substances 0.000 claims description 4
- 229920001526 metallocene linear low density polyethylene Polymers 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims description 4
- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 claims description 3
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 3
- 239000012964 benzotriazole Substances 0.000 claims description 3
- 230000002902 bimodal effect Effects 0.000 claims description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 3
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical group [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical group C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 2
- VWGKEVWFBOUAND-UHFFFAOYSA-N 4,4'-thiodiphenol Chemical compound C1=CC(O)=CC=C1SC1=CC=C(O)C=C1 VWGKEVWFBOUAND-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002530 phenolic antioxidant Substances 0.000 claims description 2
- 150000008301 phosphite esters Chemical class 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229920002050 silicone resin Polymers 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- 239000000326 ultraviolet stabilizing agent Substances 0.000 claims description 2
- 238000005187 foaming Methods 0.000 abstract description 8
- 239000000779 smoke Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 2
- 239000003431 cross linking reagent Substances 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- 229940124543 ultraviolet light absorber Drugs 0.000 abstract 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 abstract 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 abstract 1
- 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 group 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 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000012757 flame retardant agent Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical group C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 210000000497 foam cell Anatomy 0.000 description 1
- 230000003325 follicular Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a silicane self-crosslinked halogen-free flame retardant polyolefin foamed composite and a preparation method thereof. The composite comprises a grated component A, a catalytic component B and halogen-free flame retardant masterbatch according to a weight proportion of 100: (3-10): (10-60), wherein the grated component A comprises low-density polyethylene, high-strength polyethylene, high-flow polyethylene, a silane crosslinking agent, a grafting initiator, a first antioxidant, a lubricating agent and 3-aminopropyl trimethoxy silane; the catalytic component B comprises an ethylene-vinyl acetate copolymer, low-density polyethylene, a second antioxidant, a crosslinking catalyst, a foaming aid and an ultraviolet light absorber; and the halogen-free flame retardant masterbatch comprises an ethylene-octylene copolymer, a modified main flame retardant, an auxiliary flame retardant, zinc stearate and a third antioxidant. The silicane self-crosslinked halogen-free flame retardant polyolefin foamed composite has the characteristics of excellent flame retardance, low smoke and toxicity, uniformity in foaming, natural crosslinking property, high temperature resistance and the like.
Description
Technical field
The present invention relates to a kind of halogen-free anti-flaming polyolefin foam composite material and preparation method thereof, particularly a kind of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material and preparation method thereof.
Background technology
LDPE expanded plastic has excellent chemistry, physical and mechanical properties.It is tough, and flexibility is good, abrasion performance, and have excellent electrical insulating property, thermal insulation and chemical resistant properties, be widely used in many fields such as packaging, chemical industry, building, cable.One of improvement direction of LDPE expanded plastic is that exploitation is soft, flexibility is high, the closed-cell foam grade of uniform foam cell, tiny densification, particularly in recent years crosslinked foaming LDPE apply in the insulating pipe of the supply and drain water system of packaging, heat-shrinkable tube, electrical equipment insulating pipe and southern area more and more wider.It is lower then to there is temperature classification in foaming LDPE in the past, and ageing-resistant performance is bad; Easily play follicular rupture shrinkage cavity distortion during high temperature, do not possess the shortcomings such as flame retardant properties.Current each field also proposes corresponding requirement to the fire-retardant of expanded plastic material, and halide-free smokeless will be the fire-retardant development trend of polyolefin plastics.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material.
The present invention also will provide the preparation method relating to a kind of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material simultaneously.
For solving above technical problem, a kind of technical scheme that the present invention takes is: a kind of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material, it is characterized in that: comprise grafting component A, catalysis B component and halogen-free flame-retardant master batch that weight proportion is 100:3 ~ 10:10 ~ 60, wherein:
In grafting component A, each component and each composition weight proportioning are: Low Density Polyethylene 40 ~ 95 parts, high-strength polyethylene 4 ~ 40 parts, high flowing polyethylene 1 ~ 20 part, silane crosslinker 1 ~ 4 part, graft initiator 0.3 ~ 1.5 part, 0.1 ~ 5 part, the first oxidation inhibitor, lubricant 0.2 ~ 2 part and 3-aminopropyl trimethoxysilane 0.1 ~ 2 part, described Low Density Polyethylene, high-strength polyethylene and the poly total amount of high flowing are 100 parts, and the melting index of described Low Density Polyethylene is 2 ~ 6g/10min; Described high-strength polyethylene is metallocene PE or bimodal polyethylene, and its melting index is 0.1g/10min ~ 3.5g/10min, and tensile strength is greater than 35MPa; Described height flowing polyethylene is the polyethylene of melting index 20 ~ 50g/10min;
In catalysis B component, each component and each composition weight proportioning are: ethylene-vinyl acetate copolymer 5 ~ 30 parts, Low Density Polyethylene 70 ~ 95 parts, 1 ~ 10 part, the second oxidation inhibitor, crosslinking catalyst 0.2 ~ 5 part, frothing aid 0.5 ~ 10 part and UV light absorber 0.2 ~ 1 part, wherein, UV light absorber is be selected from one or more the combination in Benzotriazole Ultraviolet Stabilizer, hindered amines UV light absorber and benzophenone class UV light absorber;
In halogen-free flame-retardant master batch, each component and each composition weight proportioning are: ethylene-octene copolymer 100 parts, the modification main flame retardant 40 ~ 80 parts through coupling agent surface modification treatment, auxiliary flame retardant 10 ~ 30 parts, organic silicon fibre retardant 3 ~ 20 parts, Zinic stearas 0.2 ~ 1 part, and 0.2 ~ 0.5 part, the 3rd oxidation inhibitor, described main flame retardant be selected from ultra-fine expanded based flame retardant, phosphorus-nitrogen containing flame retardant, aluminium hydroxide and magnesium hydroxide one or more, described auxiliary flame retardant is zinc borate;
One or more independently for being selected from phenolic antioxidant, amine antioxidants, thiobisphenol kind antioxidant and phosphite ester kind antioxidant of the first described oxidation inhibitor, the second oxidation inhibitor, the 3rd oxidation inhibitor.
According to the present invention, in grafting component A, silane crosslinker can and be preferably selected from vinyltrimethoxy silane, vinyltriethoxysilane, γ-aminopropyl triethoxysilane and diethylenetriamine base propyl trimethoxy silicane one or more.In grafting component A, described graft initiator can and be preferably dicumyl peroxide or 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane or the mixture of the two.In grafting component A, described lubricant can one or more for being selected from fluoropolymer modifier, silicone master batch and stearate.
According to the present invention, in catalysis B component, described crosslinking catalyst can and be preferably selected from dibutyl tin laurate, stannous octoate and cyanacrylate one or more.In catalysis B component, described frothing aid can for being selected from one or more in Cellmic C 121, N, N' dinitroso penta methyne acid amides, modified carbonate frothing aid and mono-glycerides.
According to the present invention, in described halogen-free flame-retardant master batch, described organic silicon fibre retardant can one or more for being selected from fire-retardant silicone oil, silicone resin, silicon rubber.
According to a concrete and preferred aspect of the present invention, the preparation method of the described modification main flame retardant through coupling agent surface modification treatment is: join in homogenizer by described main flame retardant, evenly spraying into quality is under high velocity agitation the titanate coupling agent of 1% ~ 3% of main flame retardant quality or the alcoholic solution of silane coupling agent, and in the alcoholic solution of titanate coupling agent or silane coupling agent, titanate coupling agent or silane coupled agent content are 30wt% ~ 60wt%.
The present invention adopts different polyolefine to prepare grafting component A, catalysis B component and halogen-free flame-retardant master batch respectively, prepare a kind of foaming non halogen flame retardant polyolefin composite, client needs to mix by 100:3 ~ 10:10 ~ 60 different ratio according to the expansion ratio of oneself and flame retardant rating etc., through extruder for shaping, corresponding product can be obtained.
According to the present invention, various poly melting index all refers to the method with reference to ASTMD1238-98 standard, and measuring condition is value measured under 190 DEG C/2.16kg.
The another technical scheme that the present invention takes is: the preparation method of the silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material that a kind of the present invention is above-mentioned, it comprises the steps:
(1) grafting component A is prepared: by whole raw material by proportioning Homogeneous phase mixing, through the granulation of reciprocating BUSS forcing machine fusion-grafting, dry, obtain grafting component A;
(2) catalysis B component is prepared: by whole raw material by proportioning Homogeneous phase mixing, through twin screw extruder grafting granulation, dry, obtain catalyst B component;
(3) inorganic fire-retarded master batch is prepared: first join in homogenizer by main flame retardant, evenly spraying into quality is under high velocity agitation the titanate coupling agent of 1% ~ 3% of main flame retardant quality or the alcoholic solution of silane coupling agent, obtained modification main flame retardant, then according to proportioning by whole raw material Homogeneous phase mixing, through Banbury mixer banburying, obtain inorganic fire-retarded master batch;
(4) step (1) gained grafting component A, step (2) gained catalysis B component and step (3) gained halogen-free flame-retardant master batch are packed respectively, mix in described ratio during use, through extruder for shaping, obtain silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material.
Further:
In step (1), the melting temperature of BUSS machine is set to: 155 DEG C ~ 185 DEG C, compression section, homogenizing zone 195 DEG C ~ 215 DEG C, head temperature 130 DEG C ~ 145 DEG C;
In step (2), screw rod feeding section, compression section, homogenizing zone and head temperature are followed successively by 80 ~ 100 DEG C, 110 ~ 115 DEG C, 120 ~ 135 DEG C and 120 ~ 135 DEG C, avoid the too high frothing aid of temperature to go to foam in advance;
In step (3), banburying temperature is set to 130 ~ 140 DEG C, and screw rod feeding section, compression section, homogenizing zone and head temperature are followed successively by 80 ~ 100 DEG C, 110 ~ 115 DEG C, 120 ~ 135 DEG C and 120 ~ 125 DEG C.
According to the present invention, by adjusting the proportioning of grafting component A, catalysis B component and halogen-free flame-retardant master batch within the scope of the present invention, can obtain and there is different expansion ratios and the product of flame retardant rating.
The all commercially available acquisition of whole raw material of the present invention, when not illustrated, is stdn chemical product.
Due to the enforcement of above technical scheme, the present invention compared with prior art tool has the following advantages:
Polyalkene foaming matrix material provided by the invention is natural-crosslinked type, after machine-shaping, without the need to process such as further poach, naturally placement and crosslinkable under room temperature, reduce manufacturing cost, substantially increase heat resistance, and possess flame retardant resistance, and be resistant environmental low-smoke halogen-free flame, ultra-fine halogen-free flame retardants is all through surface modification treatment, good with compatible polyolefin, and fire-retardant master granule is base material ethylene-octene copolymer, more fire retardant can be filled, this foaming system uniform in foaming, and the constancy that with the addition of flame retardant materials is good, if be incubated for the tubing of buildings, greatly can reduce potential risk.
Embodiment
Embodiment 1
The present embodiment provides a kind of preparation method of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material, the raw material of employing and consumption see table 1, wherein:
In grafting component A: the melting index of Low Density Polyethylene is 4g/10min; High-strength polyethylene resin is bimodal polyethylene, and its melting index is 0.3g/10min, melt strength 35MPa; High flowing polyethylene is the polyethylene of melting index 20g/10min; Silane crosslinker is vinyltrimethoxy silane, and graft initiator is DCP, and the first oxidation inhibitor is antioxidant 300, and lubricant is PPA;
In catalysis B component: in ethylene-vinyl acetate copolymer, VA content is 28%; The melting index of Low Density Polyethylene is 4g/10min; Second oxidation inhibitor is antioxidant 1010; Crosslinking catalyst is dibutyl tin laurate; Frothing aid is the mixture of Cellmic C 121 and mono-glycerides; UV light absorber is benzotriazole category;
In halogen-free flame-retardant master batch: the melting index of ethylene-octene copolymer is 5.0g/10min, and Shore A hardness is 75; Described auxiliary flame retardant is zinc borate; Organic silicon fibre retardant is fire-retardant silicone oil, and the 3rd oxidation inhibitor is antioxidant 1010 and irgasfos 168 mixture,
Modified flame-retardant agent is prepared by following process: join in homogenizer by main flame retardant (ultra-fine expanded based flame retardant and magnesium hydroxide mass ratio are the mixture of 1 to 1), evenly spray into the alcoholic solution that quality is the titanate coupling agent of 1% of main flame retardant quality under high velocity agitation, in the alcoholic solution of titanate coupling agent, titanate coupling agent content is 30wt%.
The preparation method of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material comprises the steps:
(1) Low Density Polyethylene, high-strength polyethylene, high workability polyethylene, silane crosslinker, graft initiator, the first oxidation inhibitor, lubricant and anti-precrosslinker are pressed proportioning Homogeneous phase mixing, through the granulation of reciprocating BUSS forcing machine fusion-grafting, drying, obtains grafting component A;
(2) by ethylene-vinyl acetate copolymer, Low Density Polyethylene, the second oxidation inhibitor, crosslinking catalyst, frothing aid and UV light absorber proportioning Homogeneous phase mixing, through the granulation of twin screw extruder fusion-grafting, dry, obtain catalyst B component;
(3) ethylene-octene copolymer, modification main flame retardant, organic silicon fibre retardant, Zinic stearas and the 3rd oxidation inhibitor are mixed by proportioning, through Banbury mixer banburying, obtained inorganic fire-retarded master batch;
(4) step (1) gained grafting component A, step (2) gained catalysis B component and step (3) gained halogen-free flame-retardant master batch are packed respectively in proportion, during use, mix by weight 100:5:25, through extruder for shaping, to obtain final product.
Embodiment 2
The present embodiment provides a kind of preparation method of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material, the raw material of employing and consumption see table 1, wherein:
Wherein:
In grafting component A: Low Density Polyethylene is melting index is 2g/10min; High-strength polyethylene resin is metallocene PE, and its melting index is 3.5g/10min, tensile strength 35MPa; High flowing polyethylene is the polyethylene of melting index 20g/10min; Silane crosslinker is vinyltrimethoxy silane, and graft initiator is DCP, and the first oxidation inhibitor is antioxidant 300, and lubricant is fluoropolymer modifier;
In catalysis B component: crosslinking catalyst is stannous octoate, frothing aid is the mixture of N, N' dinitroso penta methyne acid amides and mono-glycerides, and UV light absorber is hindered amines;
In halogen-free flame-retardant master batch: in modification main flame retardant, main flame retardant is ultra-fine expanded based flame retardant and aluminium hydroxide is the mixture of 1:2 by quality; Organic silicon fibre retardant is fire-retardant silicone oil, 3rd oxidation inhibitor is antioxidant 1010 and irgasfos 168 mixture, modified flame-retardant agent is prepared by following process: joined by main flame retardant in homogenizer, evenly spray into the alcoholic solution that quality is the silane coupling agent of 2% of fire retardant quality under high velocity agitation, in the alcoholic solution of silane coupling agent, silane coupled agent content is 30wt%.
All the other raw materials are in the same manner as in Example 1.The preparation process of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material is with embodiment 1, and wherein, the weight ratio of grafting component A, catalysis B component and halogen-free flame-retardant master batch is that 100:9:10 different ratio mixes, and through extruder for shaping, to obtain final product.
Embodiment 3
The present embodiment provides a kind of preparation method of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material, the raw material of employing and consumption see table 1, wherein:
In grafting component A: Low Density Polyethylene is melting index is 6g/10min; High flowing polyethylene is the polyethylene of melting index 50g/10min; Silane crosslinker is vinyltrimethoxy silane, and graft initiator is 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane, and the first oxidation inhibitor is antioxidant 300;
In catalysis B component: frothing aid is the mixture in modified carbonate frothing aid and mono-glycerides, and UV light absorber is benzophenone class;
In halogen-free flame-retardant master batch: in modification main flame retardant, main flame retardant is that to be selected from nitrogen phosphorus system's based flame retardant and magnesium hydroxide be the mixture of 1:0.5 in mass ratio, preparation method is as follows for modification main flame retardant: joined by main flame retardant in homogenizer, evenly spray into the alcoholic solution that quality is the titanate coupling agent of 2% of fire retardant quality under high velocity agitation, in the alcoholic solution of titanate coupling agent, titanate coupling agent content is 45wt%.Organic silicon fibre retardant is fire-retardant silicone oil, and the 3rd oxidation inhibitor is antioxidant 1010 and irgasfos 168 mixture.
The preparation process of all the other raw materials silane self-crosslinking in the same manner as in Example 1 halogen-free anti-flaming polyolefin foam composite material is with embodiment 1.Wherein, the weight ratio of grafting component A, catalysis B component and halogen-free flame-retardant master batch is that 100:4:15 different ratio mixes, and through extruder for shaping, to obtain final product.
Embodiment 4
The present embodiment provides a kind of preparation method of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material, the raw material of employing and consumption see table 1, wherein:
In grafting component A: Low Density Polyethylene is melting index is 4g/10min; High-strength polyethylene resin is metallocene PE, and its melting index is 3.5g/10min, and tensile strength is more than or equal to 35MPa; High flowing polyethylene is the polyethylene of melting index 20g/10min; Silane crosslinker is vinyltrimethoxy silane, and graft initiator is DCP, and the first oxidation inhibitor is antioxidant 300, and lubricant is fluoropolymer modifier;
In catalysis B component: crosslinking catalyst is stannous octoate, frothing aid is the mixture of N, N' dinitroso penta methyne acid amides and mono-glycerides, and UV light absorber is hindered amines;
In halogen-free flame-retardant master batch: the main flame retardant of modification main flame retardant is the mixture of nitrogen phosphorus system's based flame retardant and aluminium hydroxide 1:1 in mass ratio, be prepared as follows: main flame retardant is joined in homogenizer, evenly spray into the alcoholic solution that quality is the silane coupling agent of fire retardant quality 2% under high velocity agitation, in the alcoholic solution of silane coupling agent, silane coupled agent content is 60wt%.Organic silicon fibre retardant is fire-retardant silicone oil, and the 3rd oxidation inhibitor is antioxidant 1010 and irgasfos 168 mixture.
All the other raw materials are in the same manner as in Example 1.The preparation process of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material is with embodiment 1.Wherein, the weight ratio of grafting component A, catalysis B component and halogen-free flame-retardant master batch is that 100:6:15 different ratio mixes, and through extruder for shaping, to obtain final product.
The raw material composition of table 1 embodiment 1 ~ 4
The properties of embodiment 1 ~ 4 silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material is tested.Result is see table 2.For ease of comparing, also list the desired value of this material company standard defined in table 2.
Table 2 embodiment 1 ~ 4 silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material performance
Above to invention has been detailed description; its object is to allow the personage being familiar with this art can understand content of the present invention and be implemented; can not limit the scope of the invention with this; and the invention is not restricted to the embodiments described; the equivalence change that all spirit according to the present invention are done or modification, all should be encompassed in protection scope of the present invention.
Claims (9)
1. a silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material, is characterized in that: comprise grafting component A, catalysis B component and halogen-free flame-retardant master batch that weight proportion is 100:3 ~ 10:10 ~ 60, wherein:
In grafting component A, each component and each composition weight proportioning are: Low Density Polyethylene 40 ~ 95 parts, high-strength polyethylene 4 ~ 40 parts, high flowing polyethylene 1 ~ 20 part, silane crosslinker 1 ~ 4 part, graft initiator 0.3 ~ 1.5 part, 0.1 ~ 5 part, the first oxidation inhibitor, lubricant 0.2 ~ 2 part and 3-aminopropyl trimethoxysilane 0.1 ~ 2 part, described Low Density Polyethylene, high-strength polyethylene and the poly total amount of high flowing are 100 parts, and the melting index of described Low Density Polyethylene is 2 ~ 6g/10min; Described high-strength polyethylene is metallocene PE or bimodal polyethylene, and its melting index is 0.1g/10min ~ 3.5g/10min, and tensile strength is greater than 35MPa; Described height flowing polyethylene is the polyethylene of melting index 20 ~ 50g/10min, described silane crosslinker be selected from vinyltrimethoxy silane, vinyltriethoxysilane, γ-aminopropyl triethoxysilane and diethylenetriamine base propyl trimethoxy silicane one or more;
In catalysis B component, each component and each composition weight proportioning are: ethylene-vinyl acetate copolymer 5 ~ 30 parts, Low Density Polyethylene 70 ~ 95 parts, 1 ~ 10 part, the second oxidation inhibitor, crosslinking catalyst 0.2 ~ 5 part, frothing aid 0.5 ~ 10 part and UV light absorber 0.2 ~ 1 part, wherein, UV light absorber is be selected from one or more the combination in Benzotriazole Ultraviolet Stabilizer, hindered amines UV light absorber and benzophenone class UV light absorber;
In halogen-free flame-retardant master batch, each component and each composition weight proportioning are: ethylene-octene copolymer 100 parts, the modification main flame retardant 40 ~ 80 parts through coupling agent surface modification treatment, auxiliary flame retardant 10 ~ 30 parts, organic silicon fibre retardant 3 ~ 20 parts, Zinic stearas 0.2 ~ 1 part, and 0.2 ~ 0.5 part, the 3rd oxidation inhibitor, described main flame retardant be selected from ultra-fine expanded based flame retardant, phosphorus-nitrogen containing flame retardant, aluminium hydroxide and magnesium hydroxide one or more, described auxiliary flame retardant is zinc borate;
One or more independently for being selected from phenolic antioxidant, amine antioxidants, thiobisphenol kind antioxidant and phosphite ester kind antioxidant of the first described oxidation inhibitor, the second oxidation inhibitor, the 3rd oxidation inhibitor.
2. silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material according to claim 1, it is characterized in that: in grafting component A, described graft initiator is dicumyl peroxide or 2,5-dimethyl-2,5-bis(t-butylperoxy) hexane or the mixture of the two.
3. silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material according to claim 1, is characterized in that: in grafting component A, described lubricant be selected from fluoropolymer modifier, silicone master batch and stearate one or more.
4. silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material according to claim 1, it is characterized in that: in catalysis B component, described crosslinking catalyst be selected from dibutyl tin laurate, stannous octoate and cyanacrylate one or more.
5. silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material according to claim 1, it is characterized in that: in catalysis B component, described frothing aid is for being selected from one or more in Cellmic C 121, N, N'-dinitroso penta methyne acid amides, modified carbonate frothing aid and mono-glycerides.
6. silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material according to claim 1, is characterized in that: in described halogen-free flame-retardant master batch, described organic silicon fibre retardant be selected from fire-retardant silicone oil, silicone resin, silicon rubber one or more.
7. silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material according to claim 1, it is characterized in that: the preparation method of the described modification main flame retardant through coupling agent surface modification treatment is: join in homogenizer by described main flame retardant, evenly spraying into quality is under high velocity agitation the titanate coupling agent of 1% ~ 3% of main flame retardant quality or the alcoholic solution of silane coupling agent, and in the alcoholic solution of titanate coupling agent or silane coupling agent, titanate coupling agent or silane coupled agent content are 30wt% ~ 60wt%.
8. a preparation method for the silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material any one of claim 1 to 7 described in claim, is characterized in that: comprise the steps:
(1) grafting component A is prepared: by whole raw material by proportioning Homogeneous phase mixing, through the granulation of reciprocating BUSS forcing machine fusion-grafting, dry, obtain grafting component A;
(2) catalysis B component is prepared: by whole raw material by proportioning Homogeneous phase mixing, through twin screw extruder grafting granulation, dry, obtain catalyst B component;
(3) inorganic fire-retarded master batch is prepared: first join in homogenizer by main flame retardant, evenly spraying into quality is under high velocity agitation the titanate coupling agent of 1% ~ 3% of main flame retardant quality or the alcoholic solution of silane coupling agent, obtained modification main flame retardant, then according to proportioning by whole raw material Homogeneous phase mixing, through Banbury mixer banburying, obtain inorganic fire-retarded master batch;
(4) step (1) gained grafting component A, step (2) gained catalysis B component and step (3) gained halogen-free flame-retardant master batch are packed respectively, mix in described ratio during use, through extruder for shaping, obtain silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material.
9. the preparation method of silane self-crosslinking halogen-free anti-flaming polyolefin foam composite material according to claim 8, is characterized in that:
In step (1), the melting temperature of BUSS machine is set to: 155 DEG C ~ 185 DEG C, compression section, homogenizing zone 195 DEG C ~ 215 DEG C, head temperature 130 DEG C ~ 145 DEG C;
In step (2), screw rod feeding section, compression section, homogenizing zone and head temperature are followed successively by 80 ~ 100 DEG C, 110 ~ 115 DEG C, 120 ~ 135 DEG C and 120 ~ 135 DEG C, avoid the too high frothing aid of temperature to go to foam in advance;
In step (3), banburying temperature is set to 130 ~ 140 DEG C, and screw rod feeding section, compression section, homogenizing zone and head temperature are followed successively by 80 ~ 100 DEG C, 110 ~ 115 DEG C, 120 ~ 135 DEG C and 120 ~ 125 DEG C.
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