CN116836539A - Self-reinforced halogen-free flame-retardant polyurethane composite material in damp and hot environment and preparation method and application thereof - Google Patents
Self-reinforced halogen-free flame-retardant polyurethane composite material in damp and hot environment and preparation method and application thereof Download PDFInfo
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 82
- 239000004814 polyurethane Substances 0.000 title claims abstract description 82
- 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 71
- 239000002131 composite material Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000004432 silane-modified polyurethane Substances 0.000 claims abstract description 33
- 239000004721 Polyphenylene oxide Substances 0.000 claims abstract description 19
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 229920000570 polyether Polymers 0.000 claims abstract description 19
- 229910000077 silane Inorganic materials 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 17
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 16
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 13
- 229920003225 polyurethane elastomer Polymers 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 239000000314 lubricant Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003607 modifier Substances 0.000 claims abstract description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 3
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 3
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims description 12
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 claims description 12
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 10
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- REBHQKBZDKXDMN-UHFFFAOYSA-M [PH2]([O-])=O.C(C)[Al+]CC Chemical compound [PH2]([O-])=O.C(C)[Al+]CC REBHQKBZDKXDMN-UHFFFAOYSA-M 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 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 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 238000007792 addition Methods 0.000 description 5
- -1 polyethylene Polymers 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000006378 damage Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 2
- 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 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 2
- 229910001377 aluminum hypophosphite Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
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- 238000004898 kneading Methods 0.000 description 1
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- 230000002787 reinforcement Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect 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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
-
- 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
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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 belongs to the technical field of polyurethane composite materials, and relates to a self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment, and a preparation method and application thereof. The invention discloses a self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment, which comprises the following components in parts by weight: 70-90 parts of polyurethane elastomer, 10-30 parts of silane end-capped modified polyurethane, 15-30 parts of compound efficient flame retardant, 0.5-2 parts of lubricant and 0.5-2 parts of antioxidant. The invention also discloses a preparation method of the self-reinforced halogen-free flame-retardant polyurethane composite material in a damp-heat environment, which comprises the following steps: s1, preparing silane modified polyurethane: heating and mixing polyether polyol and diisocyanate, and then dripping a silane modifier until the system is free of isocyanate groups, thus obtaining the modified polyurethane foam; s2, mixing all the raw materials, feeding the mixture into a double-screw extruder, extruding, granulating and drying to obtain a composite material; the self-reinforced halogen-free flame-retardant polyurethane composite material in the hot and humid environment can be applied to the field of cables.
Description
Technical Field
The invention belongs to the technical field of polyurethane composite materials, and relates to a self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment, and a preparation method and application thereof.
Background
The material commonly used at present is thermoplastic polyurethane elastomer (TPU), which has good mechanical properties, excellent wear resistance and good mechanical properties still kept in high and low temperature environments, but has higher hardness, poor flame retardance and poor water resistance, and the problems limit the application range. In the national standard of new GB/T33594-2017 electric automobile charging cable, hydrolysis resistance requires that the polyurethane composite cable material can withstand 80 ℃ water boiling for 168 hours, and the change rate of tensile strength and elongation at break is within +/-30 percent. The polyester polyurethane is not hydrolysis-resistant, and a carbodiimide molecular chain repairing agent is often added when the polyester polyurethane is used as a cable material, but the polyester polyurethane can be rapidly degraded along with the consumption of the molecular chain repairing agent in a hot water environment for a long time; polyether polyurethane has good hydrolysis resistance, but when the polyether polyurethane is used as a cable, a large amount of flame retardant is often required to be added into the polyether polyurethane, the permeation of moisture into the polyurethane is quickened at the interface generated by the flame retardant, so that the polyurethane material is softened, meanwhile, the moisture can replace hydrogen bonds in polyurethane molecules and among molecular chains, microphase separation of the polyurethane is weakened, and the mechanical property is greatly reduced.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a self-reinforced halogen-free flame-retardant polyurethane composite material in a damp-heat environment, which can keep better mechanical properties in the damp-heat environment, can realize flame retardant effect by adding less flame retardant, and expands the application of the polyurethane composite material.
The aim of the invention can be achieved by the following technical scheme:
the self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment comprises the following components in parts by weight:
70-90 parts of polyurethane elastomer, 10-30 parts of silane end-capped modified polyurethane, 15-30 parts of compound efficient flame retardant, 0.5-2 parts of lubricant and 0.5-2 parts of antioxidant.
In the existing polyurethane materials, a large amount of flame retardant is generally needed to be added to achieve the aim of flame retardance, but the addition of the large amount of flame retardant causes the polyurethane materials to soften in a damp-heat environment, so that the hydrolysis resistance of polyether polyurethane is reduced, and the mechanical property is greatly reduced; the raw material system of the invention adopts a system compounded by silane end-capped modified polyurethane and polyurethane elastomer as a matrix, alkoxy groups in the system are gradually crosslinked and solidified in a high-temperature and high-humidity environment to form a micro-crosslinked interpenetrating network structure, and the mechanical property reduced by softening of water on polyurethane and destruction of hydrogen bonds among polyurethane molecules by water is compensated; the flame retardant can meet the flame retardant performance requirement only by adding a small amount of flame retardant into the system, and the reduction of the retention rate of the mechanical performance caused by the addition of the flame retardant can be improved, so that the polyurethane composite material has better mechanical performance while meeting the flame retardant performance.
Preferably, the silane modified polyurethane is added in an amount of 5 to 20 percent in the raw material system.
Preferably, the addition amount of the compound efficient flame retardant in the raw material system is 10-20%.
Further preferably, the mass ratio of the silane modified polyurethane to the compound efficient flame retardant is (0.5-1.2): 1.
preferably, the silane-modified polyurethane is prepared by modifying an isocyanate-terminated polyurethane prepolymer with a silane modifier.
The isocyanate end-capped polyurethane prepolymer is an intermediate reactant for synthesizing silane end-capped polyurethane, has high isocyanate activity, can react with a silane coupling agent with amino groups, and has simple reaction process and low raw material cost compared with other reactions.
Further preferably, the molar ratio of the silane modifier to the isocyanate terminated polyurethane prepolymer is (1.01 to 1.2): 1.
preferably, the isocyanate-terminated polyurethane prepolymer is obtained by heat mixing a polyether polyol with a diisocyanate.
Further preferably, the ratio of NCO/OH in the polyether polyol and the diisocyanate is (1.1 to 1.8): 1.
more preferably, the heating temperature is 60 to 80 ℃ and the time is 1 to 8 hours.
Preferably, the silane modifier is one or more of amino-containing silane coupling agents such as KH550, KH792, KH-602, etc.
Preferably, the polyether polyol has a molecular weight of 1000 to 8000; the diisocyanate is one or more of MDI, TDI, HDI.
Preferably, the high-efficiency compound flame retardant comprises (2-6): 1-3): 1 diethyl aluminum phosphinate (ADP), piperazine pyrophosphate (PAPP) and Melamine Cyanurate (MCA) in mass ratio.
Preferably, the polyurethane resin is a polyether polyurethane elastomer.
Preferably, the lubricant is a low molecular wax or silicone powder dispersant.
Preferably, the antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and/or a mixture of antioxidant 1076 and antioxidant 168.
The invention also discloses a preparation method of the self-reinforced halogen-free flame-retardant polyurethane composite material in a damp-heat environment, which comprises the following steps:
s1, preparing silane modified polyurethane: heating and mixing polyether polyol and diisocyanate, and then dripping a silane modifier until the system is free of isocyanate groups, thus obtaining the modified polyurethane foam;
s2, mixing all the raw materials, feeding the mixture into a double-screw extruder, extruding, granulating and drying to obtain the composite material.
Preferably, the isocyanate group content in the isocyanate-terminated polyurethane prepolymer is measured in step S1 by di-n-butylamine back titration.
Further preferably, the twin-screw kneading extruder temperature is 180 to 210 ℃.
The invention also discloses application of the self-reinforced halogen-free flame-retardant polyurethane composite material in the field of cables in a wet and hot environment.
Preferably, the mechanical property of the composite material in a damp-heat environment is 80-105% of the mechanical property of the composite material in a normal-temperature environment.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention adopts silane end-capped modified polyurethane and polyurethane to blend as a resin system matrix, alkoxy groups on silane end-capped polyurethane end-capped silane in the system are gradually crosslinked and cured in a high-temperature and high-humidity environment to form a micro-crosslinked interpenetrating network structure, and the mechanical property reduced by softening of water on polyurethane and destruction of hydrogen bonds among polyurethane molecules by water is compensated; namely, the wet and hot environment can provide good conditions for silane crosslinking and curing, so that the polyurethane composite material can keep good mechanical properties in the wet and hot environment.
2. The silane modified polyurethane is added into the self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment, so that the flexibility of the polyurethane composite material can be improved, and the problems of high hardness and poor flexibility of the polyurethane material as a cable material are solved.
3. The flame retardant added in the self-reinforced halogen-free flame-retardant polyurethane composite material under the damp and hot environment is a flame retardant compounded by piperazine pyrophosphate, diethyl aluminum hypophosphite and melamine cyanurate, and has good synergistic flame retardant effect, and the flame retardant performance can pass a GB/T2408V-0 vertical combustion test under the condition of less total addition.
4. According to the self-reinforced halogen-free flame-retardant polyurethane composite material under the damp and hot environment, a small amount of compound flame retardant is added into the polyurethane elastomer and silane modified polyurethane compound system, so that the polyurethane composite material has good mechanical property while meeting the flame retardant property.
5. When the self-reinforced halogen-free flame-retardant polyurethane composite material in the damp and hot environment is applied to the field of cables, the self-reinforced halogen-free flame-retardant polyurethane composite material has better environmental applicability and effectively expands the application range.
Detailed Description
The following are specific examples of the present invention, and the technical solutions of the present invention are further described, but the present invention is not limited to these examples.
Unless otherwise indicated, all materials used in the present invention are commercially available and methods are well known to those skilled in the art.
The preparation method of the silane modified polyurethane comprises the following steps:
(1) At N 2 Under the protection, polyether polyol and diisocyanate are heated and mixed, and the ratio of NCO/OH added is (1.1-1.8): 1, stirring until the hydroxyl is reacted completely;
(2) And (3) dripping a silane modifier into the mixture, determining the content of isocyanate groups in the isocyanate-terminated polyurethane prepolymer by using a di-n-butylamine back titration method, and stirring until the system does not have isocyanate groups, thus obtaining the silane modified polyurethane.
The self-reinforced halogen-free flame-retardant polyurethane composite material in the damp and hot environment comprises the following raw materials: 70-90 parts of polyurethane elastomer, 10-30 parts of silane modified polyurethane, 15-30 parts of compound efficient flame retardant, 0.5-2 parts of lubricant and 0.5-2 parts of antioxidant;
and (3) mixing the raw materials, feeding the mixture into a double-screw extruder, extruding, granulating and drying to obtain the composite material.
The polyurethane resin is polyether polyurethane elastomer;
the lubricant is low molecular wax and silicone powder dispersant;
the antioxidant is a mixture of antioxidant 1010 and antioxidant 168, and/or a mixture of antioxidant 1076 and antioxidant 168;
the high-efficiency compound flame retardant comprises (2-6) 1-3 of diethyl aluminum phosphinate (ADP), piperazine pyrophosphate (PAPP) and Melamine Cyanurate (MCA) in mass ratio;
the molecular weight of the polyether polyol is 1000-8000;
the diisocyanate is one or more of MDI, TDI, HDI.
The silane modifier is one or more of amino-containing silane coupling agents such as KH550, KH792, KH-602, etc.
Example 1
Preparation of silane-modified polyurethane in this example:
(1) Drying polyether polyol (PTMEG, molecular weight 3000) at 110deg.C under reduced pressure for 3 hr to remove water, and cooling to reaction temperature (80deg.C); adding diisocyanate (MDI), in N 2 Stirring and reacting for 3 hours at 80 ℃ under the protection, wherein the ratio of the added NCO/OH is 1.5:1; synthesizing an isocyanate-terminated polyurethane prepolymer;
(2) Adding a silane modifier KH550 dropwise into the mixture, wherein the molar ratio of KH550 to isocyanate in the mixture is 1:1.05; after the dripping is finished, stirring at a constant speed at room temperature for reaction for 3 hours, and determining the content of isocyanate groups in the isocyanate-terminated polyurethane prepolymer by using a di-n-butylamine back titration method until the system has no isocyanate groups, thus obtaining the silane modified polyurethane.
The raw materials of the self-reinforced halogen-free flame-retardant polyurethane composite material in the damp and hot environment comprise: 80 parts of polyurethane elastomer, 20 parts of silane modified polyurethane, 22 parts of compound efficient flame retardant (12 parts of ADP,7 parts of PAPP,3 parts of MCA), 1.5 parts of lubricant (polyethylene wax) and 1.5 parts of antioxidant (1 part of antioxidant 1010,0.5 parts of antioxidant 168);
mixing the raw materials at a low speed at 110 ℃ for 5min, feeding the mixture into a double-screw extruder, extruding, granulating and drying to obtain a composite material; wherein the temperature 1 to 10 zones of the twin-screw extruder are set as follows: 150 ℃,160 ℃,165 ℃,175 ℃,185 ℃,185 ℃,185 ℃,180 ℃,175 ℃,170 ℃.
The performances of the prepared self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment are shown in table 1.
Example 2
Compared with the embodiment 1, the difference is that the self-reinforced halogen-free flame retardant polyurethane composite material under the damp and hot environment comprises the following raw materials:
78 parts of polyurethane elastomer, 23 parts of silane modified polyurethane, 20 parts of compound efficient flame retardant (10 parts of ADP,6 parts of PAPP,4 parts of MCA), 1 part of lubricant (polyethylene wax), 2 parts of antioxidant (1 part of antioxidant 1076,1 parts of antioxidant 168).
The performances of the prepared self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment are shown in table 1.
Example 3
Compared with the embodiment 1, the difference is that the self-reinforced halogen-free flame retardant polyurethane composite material under the damp and hot environment comprises the following raw materials:
90 parts of polyurethane elastomer, 10 parts of silane modified polyurethane, 22 parts of compound efficient flame retardant (12 parts of ADP,7 parts of PAPP,3 parts of MCA), 1.5 parts of lubricant (polyethylene wax) and 1.5 parts of antioxidant (1 part of antioxidant 1010,0.5 parts of antioxidant 168).
The performances of the prepared self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment are shown in table 1.
Example 4
Compared with the embodiment 1, the difference is that the self-reinforced halogen-free flame retardant polyurethane composite material under the damp and hot environment comprises the following raw materials:
70 parts of polyurethane elastomer, 30 parts of silane modified polyurethane, 22 parts of compound efficient flame retardant (12 parts of ADP,7 parts of PAPP,3 parts of MCA), 1.5 parts of lubricant (polyethylene wax) and 1.5 parts of antioxidant (1 part of antioxidant 1010,0.5 parts of antioxidant 168).
The performances of the prepared self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment are shown in table 1.
Example 5
Compared with the embodiment 1, the difference is that the self-reinforced halogen-free flame retardant polyurethane composite material under the damp and hot environment comprises the following raw materials:
95 parts of polyurethane elastomer, 5 parts of silane modified polyurethane, 22 parts of compound efficient flame retardant (12 parts of ADP,7 parts of PAPP,3 parts of MCA), 1.5 parts of lubricant (polyethylene wax) and 1.5 parts of antioxidant (1 part of antioxidant 1010,0.5 parts of antioxidant 168).
The performances of the prepared self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment are shown in table 1.
Example 6
In comparison with example 1, the difference is that in the preparation of the silane-modified polyurethane, the NCO/OH feed ratio is 2:1.
example 7
In comparison with example 1, the difference is that in the preparation of the silane-modified polyurethane, the NCO/OH feed ratio is 1.1:1.
example 8
The difference compared to example 1 is that in the preparation of the silane-modified polyurethane, the molecular weight of the polyether diol PTMEG is 5000.
Comparative example 1
The difference compared with example 1 is that no silane-modified polyurethane is added, the proportions of the remaining components in the system being unchanged.
The properties of the polyurethane composite material obtained are shown in Table 1.
Comparative example 2
The difference compared to example 1 is that the flame retardant is only ADP.
The properties of the polyurethane composite material obtained are shown in Table 1.
Comparative example 3
The difference compared to example 1 is that no flame retardant is added and the proportions of the remaining components in the system are unchanged.
Table 1, performance table of polyurethane composite
According to the table, the self-reinforced halogen-free flame-retardant polyurethane composite material has good mechanical property and flame retardant property in a hot and humid environment, and can still keep 80-105% of mechanical property in the hot and humid environment, so that the material has good service life when being applied to the cable field, and can adapt to more scenes.
In example 4, the silane-modified polyurethane content was too high (24%), and the mechanical properties were reduced due to the low molecular weight of the silane-modified polyurethane relative to the commercial polyurethane, while the vertical combustion performance could only reach V-2 due to the presence of droplets in the vertical combustion test due to the relatively small molecular weight; in the embodiment 5, the content of the silane modified polyurethane is too low (4%), so that the silane modified polyurethane cannot be crosslinked in a system to form a cured network, and the mechanical property is reduced after the wet heat aging;
in the preparation of the silane-modified polyurethane in example 6, the NCO/OH feed ratio was 2:1, the synthesized silane modified polyurethane with low molecular weight is subjected to terminal group alkoxy hydrolysis and crosslinking to form a network in a wet and hot environment, so that the mechanical property reduction caused by the damage of polyurethane hydrogen bonds by moisture is enhanced, if the NCO/OH feeding ratio is continuously increased, the isocyanate content is gradually increased, the diisocyanate exists in a small molecular form in a system, the plasticizing-like effect is achieved, and the mechanical property is further reduced; the NCO/OH ratio of example 7 was 1.1:1, resulting in an increase in the reaction time during the preparation process, but a less pronounced change in properties.
In comparative example 1, the silane-modified polyurethane is not added to soften the polyurethane by moisture, and the hydrogen bond between the polyurethanes is broken, but silane crosslinking reinforcement is not obtained, so that the mechanical properties are greatly reduced; in comparative example 2, the compound flame retardant is not added, and only ADP is used as the flame retardant, so that the flame retardant effect can only reach V-2, the mechanical property is slightly reduced, and if the flame retardant effect of V-0 is required to be achieved, more ADP is required to be added, but the mechanical property is greatly influenced; in comparative example 3, no flame retardant is added, the existence of interfaces in the system is reduced, channels for water penetration are reduced, and the mechanical properties after humid heat aging are improved, but the high-efficiency flame retardant performance required by the invention cannot be realized.
In summary, the silane modified polyurethane and polyurethane are adopted to be blended as a resin system matrix, alkoxy groups in the system are gradually crosslinked and cured in a high-temperature and high-humidity environment to form a micro-crosslinked interpenetrating network structure, and the mechanical properties reduced due to the softening of water to polyurethane and the damage of hydrogen bonds among polyurethane molecules by water are compensated; and only a small amount of compound flame retardant is needed to be added in the system, so that the polyurethane composite material can meet the flame retardant property and avoid the influence of hydrolysis on the mechanical property.
The specific embodiments described herein are offered by way of example only to illustrate the spirit of the invention. Those skilled in the art may make various modifications or additions to the described embodiments or substitutions thereof without departing from the spirit of the invention or exceeding the scope of the invention as defined in the accompanying claims.
Claims (10)
1. The self-reinforced halogen-free flame-retardant polyurethane composite material in a damp and hot environment is characterized by comprising the following components in parts by weight:
70-90 parts of polyurethane elastomer, 10-30 parts of silane modified polyurethane, 15-30 parts of compound efficient flame retardant, 0.5-2 parts of lubricant and 0.5-2 parts of antioxidant.
2. The self-reinforced halogen-free flame-retardant polyurethane composite material under the damp and hot environment according to claim 1, wherein the addition amount of silane modified polyurethane in a raw material system is 5-20%.
3. The self-reinforced halogen-free flame retardant polyurethane composite material under the damp and hot environment according to claim 1, wherein the addition amount of the compound efficient flame retardant in a raw material system is 10-20%.
4. The self-reinforced halogen-free flame retardant polyurethane composite material under the damp and hot environment according to claim 1, wherein the silane modified polyurethane is prepared by modifying isocyanate terminated polyurethane prepolymer by a silane modifier; the molar ratio of the two is (1.01-1.2): 1.
5. the self-reinforced halogen-free flame retardant polyurethane composite material under the damp and hot environment according to claim 4, wherein the isocyanate terminated polyurethane prepolymer is obtained by heating and mixing polyether polyol and diisocyanate.
6. The self-reinforced halogen-free flame retardant polyurethane composite material under the damp and hot environment according to claim 5, wherein the ratio of NCO/OH in polyether polyol and diisocyanate is (1.1-1.8): 1.
7. the self-reinforced halogen-free flame retardant polyurethane composite material under the damp and hot environment according to claim 6, wherein the molecular weight of the polyether polyol is 1000-8000; the diisocyanate is one or more of MDI, TDI, HDI.
8. The self-reinforced halogen-free flame-retardant polyurethane composite material in the damp and hot environment according to claim 1, wherein the high-efficiency compound flame retardant is characterized by comprising (2-6): (1-3): 1 of diethyl aluminum phosphinate (ADP), piperazine pyrophosphate (PAPP) and Melamine Cyanurate (MCA).
9. The method for preparing the self-reinforced halogen-free flame-retardant polyurethane composite material in the hot and humid environment according to claim 1, which is characterized in that the method comprises the following steps:
s1, preparing silane modified polyurethane: heating and mixing polyether polyol and diisocyanate, and then dripping a silane modifier until the system is free of isocyanate groups, thus obtaining the modified polyurethane foam;
s2, mixing all the raw materials, feeding the mixture into a double-screw extruder, extruding, granulating and drying to obtain the composite material.
10. The use of the self-reinforced halogen-free flame retardant polyurethane composite material in a hot and humid environment according to claim 1 in the field of cables.
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