CN117229584B - Environment-friendly flame-retardant waterproof material and preparation method and application thereof - Google Patents
Environment-friendly flame-retardant waterproof material and preparation method and application thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 126
- 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 120
- 239000000463 material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229920000092 linear low density polyethylene Polymers 0.000 claims abstract description 40
- 239000004707 linear low-density polyethylene Substances 0.000 claims abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000004709 Chlorinated polyethylene Substances 0.000 claims abstract description 31
- 239000012188 paraffin wax Substances 0.000 claims abstract description 28
- MWFNQNPDUTULBC-UHFFFAOYSA-N phosphono dihydrogen phosphate;piperazine Chemical compound C1CNCCN1.OP(O)(=O)OP(O)(O)=O MWFNQNPDUTULBC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000006229 carbon black Substances 0.000 claims abstract description 26
- 229920001912 maleic anhydride grafted polyethylene Polymers 0.000 claims abstract description 24
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 230000003179 granulation Effects 0.000 claims description 24
- 238000005469 granulation Methods 0.000 claims description 24
- 238000001125 extrusion Methods 0.000 claims description 16
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 9
- 229920004482 WACKER® Polymers 0.000 claims description 8
- 229910021485 fumed silica Inorganic materials 0.000 claims description 8
- 230000002209 hydrophobic effect Effects 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims description 3
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 3
- 238000010276 construction Methods 0.000 claims description 3
- 239000000155 melt Substances 0.000 claims description 3
- 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 claims description 3
- 238000005453 pelletization Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 16
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 238000002485 combustion reaction Methods 0.000 description 10
- 239000000779 smoke Substances 0.000 description 10
- 231100000419 toxicity Toxicity 0.000 description 10
- 230000001988 toxicity Effects 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
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- 230000007613 environmental effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 238000005086 pumping Methods 0.000 description 4
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 3
- 238000000265 homogenisation Methods 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- PZZHMLOHNYWKIK-UHFFFAOYSA-N eddha Chemical compound C=1C=CC=C(O)C=1C(C(=O)O)NCCNC(C(O)=O)C1=CC=CC=C1O PZZHMLOHNYWKIK-UHFFFAOYSA-N 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
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- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of flame-retardant waterproof materials, in particular to an environment-friendly flame-retardant waterproof material, and a preparation method and application thereof. The invention provides an environment-friendly flame-retardant waterproof material which comprises the following preparation raw materials in parts by weight: 10-15 parts of chlorinated polyethylene, 70-90 parts of linear low-density polyethylene, 5-10 parts of maleic anhydride grafted polyethylene, 20-30 parts of piperazine pyrophosphate flame retardant, 3-5 parts of chlorinated paraffin, 5-10 parts of white carbon black and 3-5 parts of antioxidant. The environment-friendly flame-retardant waterproof material has excellent flame-retardant effect, excellent mechanical property, low toxicity and corrosiveness.
Description
Technical Field
The invention relates to the technical field of flame-retardant waterproof materials, in particular to an environment-friendly flame-retardant waterproof material, and a preparation method and application thereof.
Background
Along with the development of the transportation industry in China, tunnels are increasingly constructed, the functions of the tunnels in transportation are increasingly exerted, and meanwhile, the requirements on the waterproof performance of the tunnels are also increased. Waterproof boards are generally adopted for tunnel waterproofing, but for special sections (gas sections), the common waterproof boards cannot meet the requirements, and flame-retardant waterproof materials are generated. The flame retardant imparts flame retardancy to the flammable polymer, and generally includes an inorganic flame retardant, a halogen flame retardant, a phosphorus flame retardant and a silicon flame retardant, wherein the halogen flame retardant is one of the organic flame retardants with the largest yield in the world at present, and more halogen flame retardants are bromine-containing and chlorine-containing flame retardants. Most of the halogen flame retardants are organic matters and have good compatibility with main polymer materials, the halogen flame retardants serving as flame retardant additives do not have essential influence on the physical and chemical properties of the polymer materials, and in addition, the halogen flame retardants can meet the requirement of small addition amount, but can achieve extremely excellent flame retardant effect. However, once the polymer material added with the halogen flame retardant burns, a large amount of hydrogen halide gas is necessarily generated, and the gas has toxicity and corrosiveness, and is extremely easy to absorb moisture in the air to form highly corrosive halogen acid, and a large amount of salt mist is accompanied, so that the salt mist, toxic gas and corrosive gas can harm human health, and simultaneously, the gas brings great obstacle to fire extinguishing, escape and recovery work. In view of the above problems, the prior art well solves the above problems by adjusting the type of the flame retardant, but the mechanical properties thereof are not guaranteed. Therefore, a need is provided for the research of environment-friendly flame-retardant waterproof materials.
Disclosure of Invention
The invention aims to provide an environment-friendly flame-retardant waterproof material, and a preparation method and application thereof. The environment-friendly flame-retardant waterproof material has excellent flame-retardant effect, excellent mechanical property, low toxicity and corrosiveness.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an environment-friendly flame-retardant waterproof material which comprises the following preparation raw materials in parts by weight: 10-15 parts of chlorinated polyethylene, 70-90 parts of linear low-density polyethylene, 5-10 parts of maleic anhydride grafted polyethylene, 20-30 parts of piperazine pyrophosphate flame retardant, 3-5 parts of chlorinated paraffin, 5-10 parts of white carbon black and 3-5 parts of antioxidant.
Preferably, the melt flow rate of the linear low density polyethylene is 1.5-2.5 g/10min under the conditions of 2.16kg and 190 ℃.
Preferably, the grafting rate of the maleic anhydride grafted polyethylene is 0.8-1.2wt%.
Preferably, the chlorinated paraffin has a relative density of 1.65g/cm 3 The chlorine content is 68-72wt%.
Preferably, the white carbon black comprises WACKER HDK ℃ H2000 hydrophobic fumed silica.
Preferably, the antioxidant comprises one or more of antioxidant 1010, antioxidant 264, antioxidant 1076 and antioxidant 2246.
The invention also provides a preparation method of the environment-friendly flame-retardant waterproof material, which comprises the following steps:
mixing part of linear low-density polyethylene, piperazine pyrophosphate flame retardant, chlorinated polyethylene, maleic anhydride grafted polyethylene, chlorinated paraffin and white carbon black, and performing extrusion granulation to obtain pre-granulation;
and mixing the pre-pelleting, the residual linear low-density polyethylene and the antioxidant, and extruding through a die head to obtain the environment-friendly flame-retardant waterproof material.
Preferably, the extrusion granulation is carried out in a twin screw extruder;
the temperature of a main machine of the double-screw extruder is 160-200 ℃, and the rotating speed is 150-180 r/min.
Preferably, the length-diameter ratio of a screw of an extruder adopted for extrusion of the die head is 30, the frequency is 12-17 Hz, and the traction frequency is 22-25 Hz;
the temperature of the feeding area is 160-175 ℃, the temperature of the melting area is 180-195 ℃, the temperature of the homogenizing area is 195-210 ℃, the temperature of the screen changer is 200-210 ℃, and the temperature of the die head is 195-205 ℃.
The invention also provides an application of the environment-friendly flame-retardant waterproof material prepared by the technical scheme or the preparation method of the technical scheme in the field of construction.
The invention provides an environment-friendly flame-retardant waterproof material which comprises the following preparation raw materials in parts by weight: 10-15 parts of chlorinated polyethylene, 70-90 parts of linear low-density polyethylene, 5-10 parts of maleic anhydride grafted polyethylene, 20-30 parts of piperazine pyrophosphate flame retardant, 3-5 parts of chlorinated paraffin, 5-10 parts of white carbon black and 3-5 parts of antioxidant. The chlorinated polyethylene has good ageing resistance and flame retardance, and the chlorinated polyethylene and chlorinated paraffin and piperazine pyrophosphate flame retardant cooperate to improve the flame retardance of the system; the linear low-density polyethylene is used as a main material of the system, so that the mechanical property of the plate can be ensured; the maleic anhydride grafted polyethylene is prepared by introducing a strong polar maleic anhydride side group on a nonpolar polyethylene molecular main chain, can be used as a compatilizer for a piperazine pyrophosphate flame retardant and polyethylene, and can be used for modifying the interface contact of white carbon black, chlorinated paraffin and linear low-density polyethylene to increase the compatibility of the linear low-density polyethylene; the white carbon black has the characteristics of high temperature resistance and incombustibility, has strong surface adsorption force, can adsorb a gas part in a product when the waterproof board is burnt, has good dispersion performance and good stability, and can improve the fluidity of powder in a system; the piperazine pyrophosphate flame retardant is a novel nitrogen-phosphorus synergistic environment-friendly flame retardant which has excellent char formation and flame retardance, and when in combustion, a compact charring layer is formed to isolate oxygen from flame propagation, and the piperazine pyrophosphate flame retardant has the characteristics of no halogen and heavy metal elements, low density, low smoke and the like. And finally, the environment-friendly flame-retardant waterproof material has excellent flame-retardant effect, low toxicity and corrosiveness.
Detailed Description
The invention provides an environment-friendly flame-retardant waterproof material which comprises the following preparation raw materials in parts by weight: 10-15 parts of chlorinated polyethylene, 70-90 parts of linear low-density polyethylene, 5-10 parts of maleic anhydride grafted polyethylene, 20-30 parts of piperazine pyrophosphate flame retardant, 3-5 parts of chlorinated paraffin, 5-10 parts of white carbon black and 3-5 parts of antioxidant.
In the present invention, all the preparation materials are commercially available products well known to those skilled in the art unless specified otherwise.
The environment-friendly flame-retardant waterproof material comprises, by mass, 10-15 parts of chlorinated polyethylene, preferably 11-14 parts, and more preferably 12-13 parts. In the present invention, the chlorinated polyethylene is preferably CPE135A available from stone house multi-billion chemical technology limited. In the invention, the chlorinated polyethylene is a high polymer material prepared by chloridizing substitution reaction of high-density polyethylene (HDPE), has good ageing resistance and flame retardance, and cooperates with chlorinated paraffin and piperazine pyrophosphate flame retardant to improve the flame retardance of the system.
Based on the mass parts of the chlorinated polyethylene, the environment-friendly flame-retardant waterproof material comprises 70-90 parts of linear low-density polyethylene, preferably 75-85 parts, and more preferably 78-82 parts. In the invention, the melt flow rate of the linear low density polyethylene at the temperature of 190 ℃ is preferably 1.5-2.5 g/10min, more preferably 1.8-2.2 g/10min. In the present invention, the type of the linear low density polyethylene is preferably Daqing petrochemical 9047. In the invention, the linear low-density polyethylene is used as a main material of a system so as to ensure the mechanical property of the plate.
Based on the mass parts of the chlorinated polyethylene, the environment-friendly flame-retardant waterproof material comprises 5-10 parts, preferably 6-9 parts, and more preferably 7-8 parts of maleic anhydride grafted polyethylene. In the present invention, the grafting ratio of the maleic anhydride grafted polyethylene is preferably 0.8 to 1.2wt%, more preferably 0.9 to 1.1wt%, and most preferably 1.0wt%. In the present invention, the maleic anhydride grafted polyethylene is preferably ZJ-900E, a company of Jie chemical technology, inc. in Guangzhou. In the invention, the maleic anhydride grafted polyethylene introduces a strong polar maleic anhydride side group on a nonpolar polyethylene molecular main chain, can be used as a compatilizer for the piperazine pyrophosphate flame retardant and the polyethylene, and can be used for modifying the interface contact of white carbon black and chlorinated paraffin with linear low-density polyethylene to increase the compatibility of the linear low-density polyethylene.
Based on the mass parts of the chlorinated polyethylene, the environment-friendly flame-retardant waterproof material comprises 20-30 parts of piperazine pyrophosphate flame retardant, preferably 22-28 parts, and more preferably 24-26 parts. In the present invention, the piperazine pyrophosphate flame retardant is preferably NH-5000C from the chemical industry limited of england. In the invention, the piperazine pyrophosphate flame retardant is a novel nitrogen-phosphorus synergistic environment-friendly flame retardant, has excellent char formation and flame retardance, forms a compact charring layer on the surface of a product to isolate oxygen from flame propagation during combustion, and has the characteristics of no halogen or heavy metal elements, low density, low fuming and the like.
Based on the mass parts of the chlorinated polyethylene, the environment-friendly flame-retardant waterproof material comprises 3-5 parts of chlorinated paraffin, preferably 3.5-4.5 parts of chlorinated paraffin, and more preferably 3.8-4.2 parts of chlorinated paraffin. In the present invention, the chlorinated paraffin preferably has a relative density of 1.65, and the chlorine content is preferably 68 to 72%, more preferably 69 to 70%. In the present invention, the chlorinated paraffin is preferably CP-70 manufactured by Jinan Jinbang environmental protection technology Co., ltd.
Based on the mass parts of the chlorinated polyethylene, the environment-friendly flame-retardant waterproof material comprises 5-10 parts of white carbon black, preferably 6-9 parts, and more preferably 7-8 parts. In the invention, the white carbon black preferably comprises WACKER HDK ℃ H2000 hydrophobic fumed silica; the content of the silica in the WACKER HDK H2000 hydrophobic fumed silica is preferably 99.8wt%. In the invention, the white carbon black is a porous substance which has high temperature resistance and incombustibility, gas phase white carbon black is selected, the surface adsorption force is strong, and the gas part in the product can be adsorbed when the waterproof board is burnt; the dispersion performance is good, the stability is good, and the fluidity of the powder in the system can be improved.
Based on the mass parts of the chlorinated polyethylene, the environment-friendly flame-retardant waterproof material comprises 3-5 parts of antioxidant, preferably 3.5-4.5 parts, and more preferably 3.8-4.2 parts. In the invention, the antioxidant preferably comprises one or more of antioxidant 1010, antioxidant 264, antioxidant 1076 and antioxidant 2246, and when the antioxidant is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the above specific substances, and the invention can be used for mixing according to any proportion.
The invention also provides a preparation method of the environment-friendly flame-retardant waterproof material, which comprises the following steps:
mixing part of linear low-density polyethylene, piperazine pyrophosphate flame retardant, chlorinated polyethylene, maleic anhydride grafted polyethylene, chlorinated paraffin and white carbon black, and performing extrusion granulation to obtain pre-granulation;
and mixing the pre-pelleting, the residual linear low-density polyethylene and the antioxidant, and extruding through a die head to obtain the environment-friendly flame-retardant waterproof material.
The invention mixes part of linear low density polyethylene, piperazine pyrophosphate flame retardant, chlorinated polyethylene, maleic anhydride grafted polyethylene, chlorinated paraffin and white carbon black, and then performs extrusion granulation to obtain pre-granulation.
In the present invention, the mass of the partially linear low density polyethylene is 50% of the mass of the linear low density polyethylene.
In the present invention, the mixing is preferably performed under stirring conditions, and the stirring conditions are not particularly limited in the present invention, and may be performed by a process well known to those skilled in the art. In the embodiment of the invention, the stirring time is specifically 20min.
In the present invention, the extrusion granulation is preferably performed in a twin-screw extruder; the host temperature of the twin-screw extruder is preferably 160-200 ℃, more preferably 170-190 ℃, and most preferably 175-185 ℃; the rotation speed is preferably 150 to 180r/min, more preferably 160 to 170r/min, and most preferably 163 to 166r/min.
After pre-granulation is obtained, the pre-granulation, the rest linear low density polyethylene and the antioxidant are mixed, and the die head extrusion is carried out, so that the environment-friendly flame-retardant waterproof material is obtained.
In the present invention, the mixing is preferably performed under stirring, and the stirring process is not particularly limited, and may be performed by a process well known to those skilled in the art. In the embodiment of the invention, the stirring time is 3-5 min. In the present invention, the stirring is preferably performed in a silo.
In the invention, the length-diameter ratio of a screw of an extruder adopted for extrusion of the die head is preferably 30, the frequency is preferably 12-17 Hz, and more preferably 14-16 Hz; the traction frequency is preferably 22-25 Hz, more preferably 23-24 Hz; the temperature of the feeding area is preferably 160-175 ℃, and more preferably 165-170 ℃; the temperature of the melting zone is preferably 180-195 ℃, more preferably 185-190 ℃; the temperature of the homogenizing zone is preferably 195-210 ℃, more preferably 200-205 ℃; the temperature of the screen changer is preferably 200-210 ℃, more preferably 204-208 ℃; the die temperature is preferably 195 to 205 ℃, more preferably 198 to 202 ℃.
The invention also provides an application of the environment-friendly flame-retardant waterproof material prepared by the technical scheme or the preparation method of the technical scheme in the field of construction. The method of the present invention is not particularly limited, and may be carried out by methods known to those skilled in the art.
The environment-friendly flame-retardant waterproof material, the preparation method and the application thereof provided by the invention are described in detail below with reference to examples, but are not to be construed as limiting the scope of the invention.
Example 1
The preparation raw materials of the environment-friendly flame-retardant waterproof material are as follows: 10 parts of chlorinated polyethylene (CPE 135A of Shijia multi-billion chemical technology Co., ltd.), 70 parts of linear low-density polyethylene (Daqing petrochemical 9047), 10 parts of maleic anhydride grafted polyethylene (ZJ-900E of Jie chemical technology Co., ltd. In Guangzhou, the city), 30 parts of piperazine pyrophosphate flame retardant (NH-5000C of Guangzhou Eden chemical industry Co., ltd.), 4 parts of chlorinated paraffin (CP-70 produced by Jinan Jinbang environmental protection technology Co., ltd.) and 5 parts of white carbon black (WACKER HDK) H2000 hydrophobic fumed silica), and 3 parts of antioxidant (model number of antioxidant 1010);
the preparation method of the environment-friendly flame-retardant waterproof material comprises the following steps: after 35 parts by weight of linear low density polyethylene, 10 parts by weight of chlorinated polyethylene, 10 parts by weight of maleic anhydride grafted polyethylene, 30 parts by weight of piperazine pyrophosphate flame retardant, 4 parts by weight of chlorinated paraffin and 5 parts by weight of white carbon black are stirred at a high speed for 20min (stirring rotation speed is 1500 rpm), extrusion granulation is carried out in a twin-screw extruder, wherein the temperature of a main machine of the twin-screw extruder is set to 160-200 ℃ (the temperature of a feeding zone is 160 ℃, the temperature of a melting zone is 175 ℃, the temperature of a homogenizing zone is 200 ℃) and the rotation speed is 150r/min, and pre-mixed granulation is obtained.
Pumping the premixed granulation, the rest 35 parts by weight of linear low-density polyethylene and 3 parts by weight of antioxidant to a storage bin, stirring for 3min, heating by a screw, and extruding by a die head: the length-diameter ratio of the screw rod of the extruder is 30, the frequency is 12Hz, and the traction frequency is 22Hz; wherein the temperature of the feeding area is 160 ℃; the temperature of the melting zone is 180 ℃; the homogenization zone temperature was 195 ℃; the temperature of the screen changer is 200 ℃; the die head temperature is 195 ℃, and the environment-friendly flame-retardant waterproof material (flame-retardant waterproof coiled material) is obtained.
The thickness of the flame-retardant waterproof coiled material is 1.2mm.
Example 2
The preparation raw materials of the environment-friendly flame-retardant waterproof material are as follows: 13 parts of chlorinated polyethylene (CPE 135A of Shijia multi-billion chemical technology Co., ltd.), 80 parts of linear low-density polyethylene (Daqing petrochemical 9047), 8 parts of maleic anhydride grafted polyethylene (ZJ-900E of Jie chemical technology Co., ltd. In Guangzhou, the city), 25 parts of piperazine pyrophosphate flame retardant (NH-5000C of Guangzhou Eden chemical industry Co., ltd.), 3 parts of chlorinated paraffin (CP-70 produced by Jinan Jinbang environmental protection technology Co., ltd.) and 8 parts of white carbon black (WACKER HDK) H2000 hydrophobic fumed silica) and 4 parts of antioxidant (antioxidant 1010 type);
the preparation method of the environment-friendly flame-retardant waterproof material comprises the following steps: after 40 parts by weight of linear low density polyethylene, 13 parts by weight of chlorinated polyethylene, 8 parts by weight of maleic anhydride grafted polyethylene, 25 parts by weight of piperazine pyrophosphate flame retardant, 3 parts by weight of chlorinated paraffin and 8 parts by weight of white carbon black are stirred at a high speed for 20min (stirring rotation speed is 1500 rpm), extrusion granulation is carried out in a twin-screw extruder, wherein the temperature of a main machine of the twin-screw extruder is set to 160-200 ℃ (the temperature of a feeding zone is 160 ℃, the temperature of a melting zone is 175 ℃, the temperature of a homogenizing zone is 200 ℃) and the rotation speed is 165r/min, and pre-mixed granulation is obtained.
Pumping the premixed granulation, the rest 40 parts by weight of linear low-density polyethylene and 4 parts by weight of antioxidant to a storage bin, stirring for 4min, heating by a screw, and extruding by a die head: the length-diameter ratio of the screw rod of the extruder is 30, the frequency is 15Hz, and the traction frequency is 23Hz; wherein the temperature of the feeding area is 170 ℃; the melting zone temperature was 190 ℃; the homogenization zone temperature was 200 ℃; the temperature of the screen changer is 205 ℃; the die head temperature is 200 ℃, and the environment-friendly flame-retardant waterproof material (flame-retardant waterproof coiled material) is obtained.
The thickness of the flame-retardant waterproof coiled material is 1.2mm.
Example 3
The preparation raw materials of the environment-friendly flame-retardant waterproof material are as follows: 15 parts of chlorinated polyethylene (CPE 135A of Shijia multi-billion chemical technology Co., ltd.), 90 parts of linear low-density polyethylene (Daqing petrochemical 9047), 5 parts of maleic anhydride grafted polyethylene (ZJ-900E of Jie chemical technology Co., ltd. In Guangzhou, the city), 20 parts of piperazine pyrophosphate flame retardant (NH-5000C of Guangzhou Eden chemical industry Co., ltd.), 5 parts of chlorinated paraffin (CP-70 produced by Jinan Jinbang environmental protection technology Co., ltd.) and 10 parts of white carbon black (WACKER HDK) H2000 hydrophobic fumed silica and 5 parts of antioxidant (model 1010);
the preparation method of the environment-friendly flame-retardant waterproof material comprises the following steps: 45 parts by weight of linear low-density polyethylene, 15 parts by weight of chlorinated polyethylene, 5 parts by weight of maleic anhydride grafted polyethylene, 20 parts by weight of piperazine pyrophosphate flame retardant, 5 parts by weight of chlorinated paraffin and 10 parts by weight of white carbon black are stirred at a high speed for 20min (the stirring rotation speed is 1500 rpm), and then extrusion granulation is carried out in a double-screw extruder, wherein the temperature of a main machine of the double-screw extruder is 160-200 ℃ (the temperature of a feeding zone is 160 ℃, the temperature of a melting zone is 175 ℃, the temperature of a homogenizing zone is 200 ℃) and the rotation speed is 180r/min, so that pre-mixed granulation is obtained;
pumping the premixed granulation, the rest 45 parts by weight of linear low-density polyethylene and 5 parts by weight of antioxidant to a storage bin, stirring for 5min, heating by a screw, and extruding by a die head: the length-diameter ratio of the screw rod of the extruder is 30, the frequency is 17Hz, and the traction frequency is 25Hz; wherein the temperature of the feeding area is 175 ℃; the temperature of the melting zone is 195 ℃; the homogenization zone temperature was 210 ℃; the temperature of the screen changer is 210 ℃; the die head temperature is 205 ℃, and the environment-friendly flame-retardant waterproof material (flame-retardant waterproof coiled material) is obtained.
The thickness of the flame-retardant waterproof coiled material is 1.2mm.
Comparative example 1
The preparation raw materials of the flame retardant waterproof material are as follows: 90 parts of linear low-density polyethylene (Daqing petrochemical 9047), 5 parts of maleic anhydride grafted polyethylene (ZJ-900E of Jie chemical technology Co., ltd. In Guangzhou, a) 40 parts of piperazine pyrophosphate flame retardant (NH-5000C of Eddha chemical Co., ltd., a) 10 parts of white carbon black (WACKER HDK H2000 hydrophobic fumed silica) and 5 parts of antioxidant (model number of antioxidant 1010); unlike example 3, the comparative example was not added with chlorinated polyethylene and chlorinated paraffin.
The preparation method of the environment-friendly flame-retardant waterproof material comprises the following steps: 45 parts by weight of linear low-density polyethylene, 5 parts by weight of maleic anhydride grafted polyethylene, 20 parts by weight of piperazine pyrophosphate flame retardant and 10 parts by weight of white carbon black are stirred at a high speed for 20min (the stirring rotation speed is 1500 rpm), and extrusion granulation is carried out in a double-screw extruder, wherein the temperature of a host machine of the double-screw extruder is set to 160-200 ℃ (the temperature of a feeding zone is 160 ℃, the temperature of a melting zone is 175 ℃, the temperature of a homogenizing zone is 200 ℃), and the rotation speed is 180r/min, so that pre-mixed granulation is obtained.
Pumping the premixed granulation, the rest 45 parts by weight of linear low-density polyethylene and 5 parts by weight of antioxidant to a storage bin, stirring for 5min, heating by a screw, extruding by a die head, and obtaining the flame retardant waterproof material (flame retardant waterproof coiled material) according to the extrusion condition of the die head in reference example 3;
the thickness of the flame-retardant waterproof coiled material is 1.2mm.
Comparative example 2
The preparation raw materials of the flame retardant waterproof material are as follows: 90 parts by weight of linear low-density polyethylene (Daqing petrochemical 9047), 25 parts by weight of decabromodiphenyl ethane and 5 parts by weight of an antioxidant (model 1010); wherein decabromodiphenylethane is a flame retardant with the effective content of more than or equal to 99.6 percent, which is produced by Weifang eulan chemical Co.
The preparation method of the environment-friendly flame-retardant waterproof material comprises the following steps: firstly premixing 25 parts by mass of decabromodiphenyl ethane and 45 parts by weight of linear low-density polyethylene, stirring at a high speed for 20min (stirring rotation speed is 1500 rpm), and then extruding and granulating in a double-screw extruder, wherein the temperature of a main machine of the double-screw extruder is 160-200 ℃ (the temperature of a feeding zone is 160 ℃, the temperature of a melting zone is 175 ℃, the temperature of a homogenizing zone is 200 ℃), and the temperature is sequentially increased, and the rotation speed is 180r/min. Other process parameters were consistent with example 3 to obtain a flame retardant waterproof material (flame retardant waterproof roll); the thickness of the flame-retardant waterproof board is 1.2mm.
Sampling the environment-friendly flame-retardant waterproof material described in examples 1-3 and the flame retardant waterproof material described in comparative examples 1-2, and performing physical property test: wherein the tensile test and the tearing test are carried out according to the specification of GB/T18173.1, and the tensile speed is (250+/-50) mm/min; the combustion performance grade is carried out according to the specification of the flat plate-shaped building material in GB8624, and the smoke toxicity grade is carried out according to the specification of GB 20285. The physical index is as follows:
the environment-friendly flame-retardant waterproof material described in example 1 has a longitudinal tensile strength of 16.8MPa, a transverse tensile mild degree of 16.4MPa, a longitudinal elongation at break of 678%, a transverse elongation at break of 690%, a longitudinal tear strength of 92kN/m, a transverse tear strength of 90kN/m, a combustion performance grade of B and a smoke toxicity grade of t1;
the environment-friendly flame-retardant waterproof material described in example 2 has a longitudinal tensile strength of 17.1MPa, a transverse tensile mild degree of 17.0MPa, a longitudinal elongation at break of 712%, a transverse elongation at break of 743%, a longitudinal tear strength of 95kN/m, a transverse tear strength of 94kN/m, a combustion performance grade of B and a smoke toxicity grade of t1;
the environment-friendly flame-retardant waterproof material described in example 3 has a longitudinal tensile strength of 17.5MPa, a transverse tensile mild degree of 17.2MPa, a longitudinal elongation at break of 708%, a transverse elongation at break of 756%, a longitudinal tear strength of 97kN/m, a transverse tear strength of 95kN/m, a combustion performance grade of B and a smoke toxicity grade of t1;
the flame retardant waterproof material described in comparative example 1 has a longitudinal tensile strength of 13.2MPa, a transverse tensile mildness of 12.9MPa, a longitudinal elongation at break of 560%, a transverse elongation at break of 602%, a longitudinal tear strength of 68kN/m, a transverse tear strength of 60kN/m, a combustion performance grade of B, and a smoke toxicity grade of t1;
the flame retardant waterproof material described in comparative example 2 has a longitudinal tensile strength of 17.4MPa, a transverse tensile mild degree of 17.1MPa, a longitudinal elongation at break of 650%, a transverse elongation at break of 662%, a longitudinal tear strength of 90kN/m, a transverse tear strength of 88kN/m, a fire performance grade of B, and a smoke toxicity grade of- - -, wherein "- -" represents that the requirements are not satisfied.
From the results, the flame-retardant waterproof material provided by the invention has the longitudinal tensile strength of more than 16.8 MPa; the transverse tensile strength is more than 16.4 MPa; the longitudinal elongation at break is more than 678%; the transverse elongation at break is more than 690%; the longitudinal tearing strength is above 92kN/m, and the transverse tearing strength is above 90 kN/m; the combustion performance grade meets the B grade, and the smoke toxicity grade meets the t1 grade. Comparative example 1 was comparable to examples 1, 2 and 3 in flame retardant performance, but the mechanical properties were significantly reduced, without adding flame retardant components such as chlorinated polyethylene and chlorinated paraffin, and with increasing the amount of piperazine pyrophosphate flame retardant. Comparative example 2 was compared with examples 1, 2 and 3, and the flame retardant system was applied as a halogen flame retardant, and the smoke toxicity thereof was not satisfied with the t1 grade, although the mechanical properties were equivalent. The flame-retardant waterproof coiled material provided by the invention has excellent performance, good flame retardance, the combustion performance grade meets the B grade, and the toxicity of the combustion product smoke is reduced.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (9)
1. The environment-friendly flame-retardant waterproof material is characterized by being prepared from the following raw materials in parts by weight: 10-15 parts of chlorinated polyethylene, 70-90 parts of linear low-density polyethylene, 5-10 parts of maleic anhydride grafted polyethylene, 20-30 parts of piperazine pyrophosphate flame retardant, 3-5 parts of chlorinated paraffin, 5-10 parts of white carbon black and 3-5 parts of antioxidant;
the grafting rate of the maleic anhydride grafted polyethylene is 0.8-1.2wt%.
2. The environment-friendly flame-retardant waterproof material as claimed in claim 1, wherein the linear low-density polyethylene has a melt flow rate of 1.5-2.5 g/10min at the temperature of 2.16kg and 190 ℃.
3. The environment-friendly flame-retardant waterproof material as claimed in claim 1, wherein the relative density of the chlorinated paraffin is 1.65g/cm 3 The chlorine content is 68-72wt%.
4. The environment-friendly flame-retardant waterproof material according to claim 1, wherein the white carbon black comprises WACKER HDK ℃ H2000 hydrophobic fumed silica.
5. The environment-friendly flame-retardant waterproof material according to claim 1, wherein the antioxidant comprises one or more of antioxidant 1010, antioxidant 264, antioxidant 1076 and antioxidant 2246.
6. The method for preparing the environment-friendly flame-retardant waterproof material according to any one of claims 1 to 5, which is characterized by comprising the following steps:
mixing part of linear low-density polyethylene, piperazine pyrophosphate flame retardant, chlorinated polyethylene, maleic anhydride grafted polyethylene, chlorinated paraffin and white carbon black, and performing extrusion granulation to obtain pre-granulation;
and mixing the pre-pelleting, the rest linear low-density polyethylene and the antioxidant, and extruding through a die head to obtain the environment-friendly flame retardant waterproof material.
7. The method of claim 6, wherein the extrusion pelletization is performed in a twin screw extruder;
the temperature of a main machine of the double-screw extruder is 160-200 ℃, and the rotating speed is 150-180 r/min.
8. The preparation method of claim 6, wherein the length-diameter ratio of a screw of an extruder adopted for extrusion by the die head is 30, the frequency is 12-17 Hz, and the traction frequency is 22-25 Hz;
the temperature of the feeding area is 160-175 ℃, the temperature of the melting area is 180-195 ℃, the temperature of the homogenizing area is 195-210 ℃, the temperature of the screen changer is 200-210 ℃, and the temperature of the die head is 195-205 ℃.
9. The environment-friendly flame-retardant waterproof material as claimed in any one of claims 1 to 5 or the environment-friendly flame-retardant waterproof material prepared by the preparation method as claimed in any one of claims 6 to 8, and the application thereof in the field of construction.
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