CN117230644A - Preparation method of alkali-resistant flame-retardant superfine fiber synthetic leather bass - Google Patents
Preparation method of alkali-resistant flame-retardant superfine fiber synthetic leather bass Download PDFInfo
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- CN117230644A CN117230644A CN202311277261.3A CN202311277261A CN117230644A CN 117230644 A CN117230644 A CN 117230644A CN 202311277261 A CN202311277261 A CN 202311277261A CN 117230644 A CN117230644 A CN 117230644A
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- retardant
- flame
- alkali
- superfine fiber
- synthetic leather
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 139
- 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 138
- 239000003513 alkali Substances 0.000 title claims abstract description 72
- 239000000835 fiber Substances 0.000 title claims abstract description 49
- 239000002649 leather substitute Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 241000321398 Dermatolepis dermatolepis Species 0.000 title claims abstract description 18
- 239000004814 polyurethane Substances 0.000 claims abstract description 49
- 229920002635 polyurethane Polymers 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 42
- 230000008569 process Effects 0.000 claims abstract description 26
- 239000002585 base Substances 0.000 claims abstract description 17
- 229920002545 silicone oil Polymers 0.000 claims abstract description 17
- 238000005470 impregnation Methods 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 15
- 239000011574 phosphorus Substances 0.000 claims abstract description 15
- 239000002002 slurry Substances 0.000 claims abstract description 9
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007730 finishing process Methods 0.000 claims abstract description 8
- 229920001410 Microfiber Polymers 0.000 claims description 38
- 239000003658 microfiber Substances 0.000 claims description 35
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000004745 nonwoven fabric Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005096 rolling process Methods 0.000 claims description 7
- 238000007711 solidification Methods 0.000 claims description 7
- 230000008023 solidification Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 5
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004945 emulsification Methods 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 238000006386 neutralization reaction Methods 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 239000002562 thickening agent Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims 6
- 238000005554 pickling Methods 0.000 claims 1
- 239000007787 solid Substances 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 5
- 239000010985 leather Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000011151 fibre-reinforced plastic Substances 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 229920000909 polytetrahydrofuran Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- KIAWELJRPUFOPP-UHFFFAOYSA-N 1-(bromomethyl)-2,4-diisocyanatobenzene Chemical compound BrCC1=CC=C(N=C=O)C=C1N=C=O KIAWELJRPUFOPP-UHFFFAOYSA-N 0.000 description 1
- LCJLEYPRGLFMGM-UHFFFAOYSA-N 1-(chloromethyl)-2,4-diisocyanatobenzene Chemical compound ClCC1=CC=C(N=C=O)C=C1N=C=O LCJLEYPRGLFMGM-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920006306 polyurethane fiber Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Landscapes
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
Abstract
The invention relates to the field of functional synthetic leather manufacturing, in particular to a preparation method of alkali-resistant flame-retardant superfine fiber synthetic leather base. According to the invention, the reactive phosphorus-containing flame retardant and the flame-retardant silicone oil are used as flame-retardant monomers, the flame-retardant waterborne polyurethane is prepared by a one-step prepolymerization method, the alkali resistance of the phosphorus-containing flame-retardant waterborne polyurethane is improved by introducing the flame-retardant silicone oil, and the flame-retardant waterborne polyurethane prepared by using the flame-retardant waterborne polyurethane as the wet impregnation slurry has better alkali resistance. Solves the problem that the flame retardant cannot be stabilized in the process of the decrement technology. And simultaneously, the flame retardance of the superfine fiber synthetic leather bass is further improved by combining a flame retardant after-finishing process and a mode of impregnating the phosphorus-nitrogen flame retardant. The finally prepared superfine fiber synthetic leather bass meets the environmental protection requirement, has excellent flame retardance and alkali resistance, and has potential application value in the fields of automotive interiors and living leather.
Description
Technical Field
The invention relates to the field of functional synthetic leather manufacturing, in particular to a preparation method of alkali-resistant flame-retardant superfine fiber synthetic leather base.
Background
It is well known that polyurethane and ultrafine fiber nonwoven fabrics together constitute a major part of ultrafine fiber synthetic leather bass (microfiber bass for short). Both of the two materials are inflammable materials, so that the microfiber bass is extremely easy to burn in the air, a high-temperature molten drop phenomenon and a large amount of toxic gases can be generated in the combustion process, the health of people is seriously endangered, and the application of the microfiber bass is greatly limited. The development of microfiber bass which has excellent flame retardance and comprehensive performance becomes a current urgent need to overcome the problem. At present, the method for obtaining the flame-retardant microfiber bass mainly comprises three aspects of preparing flame-retardant fibers, preparing flame-retardant waterborne polyurethane and finishing flame retardance. Among them, the flame-retardant waterborne polyurethane and the method for finishing after flame retardance are paid attention to by a plurality of students due to the advantages of simple preparation process and the like.
At present, the preparation of the microfiber bass mainly comprises a granulating process, a spinning process, a non-woven fabric manufacturing process, a polyurethane impregnation process, a deweighting process, a sanding process, a functional finishing process and the like. In the process of preparing the microfiber bass, strong alkali and toluene solvents are required to be adopted for decrement, and most of flame retardants cannot exist stably through the decrement process, so that the preparation of the flame retardant bass for impregnation is difficult; with the deep focus of the environment-friendly concept, toluene is gradually eliminated due to high pollution, and reduction by using strong alkali becomes the most common method for enterprises at present, so how to prepare microfiber bass which has flame retardance and alkali resistance becomes the difficult problem of current research.
Patent number CN105442340A discloses a high flame-retardant superfine fiber synthetic leather for a high-speed train seat and a preparation method thereof, wherein the high flame-retardant superfine fiber synthetic leather is prepared by the processes of preparing carbon fiber non-woven fabrics, sizing polyvinyl alcohol, impregnating polyurethane slurry and the like, and the prepared superfine fiber synthetic leather has higher flame retardance and mechanical properties. However, the reduction treatment of strong alkali and toluene solvents is avoided, the obtained superfine fiber synthetic leather has hard hand feeling, and the application field of the superfine fiber synthetic leather is greatly limited by the high cost caused by the preparation of the carbon fiber non-woven fabric. Patent number CN105002742A discloses a preparation method of environment-friendly flame-retardant microfiber leather, which is prepared by the processes of wet impregnation of flame-retardant resin, wet solidification foaming, toluene reduction, oiling, skin kneading, release paper transfer coating and the like, solves the problem of precipitation of flame retardant on the surface of superfine fiber synthetic leather, and obtains better flame retardance. However, since the toluene is reduced by the usual method in early researches, the pollution to the environment is serious, and the alkali is gradually reduced. Patent number CN115260451a discloses a synthesis method of flame-retardant waterborne polyurethane for microfiber bass impregnation. The patent prepares the flame-retardant waterborne polyurethane by taking halogenated isocyanate as a flame-retardant monomer to participate in reaction instead of traditional isocyanate, and the flame-retardant waterborne polyurethane is applied to an impregnation process of the microfiber bass, and the obtained microfiber bass has good flame retardance and certain alkali resistance. However, the introduction of halogenated isocyanates such as bromotoluene diisocyanate and chlorotoluene diisocyanate is difficult to meet the national requirements of flame retardance and environmental protection quality of the microfiber bass.
In order to overcome the defects of the method, the alkali resistance of the phosphorus-containing flame-retardant waterborne polyurethane is improved by introducing the flame-retardant silicone oil, and the flame-retardant microfiber base prepared by taking the flame-retardant silicone oil as the impregnating slurry has better alkali resistance. The problem that the flame retardant cannot be stably existing in the process of the reduction process is solved, and meanwhile, the adopted flame retardant monomers are halogen-free, so that the flame retardant can meet the environmental protection requirement and simultaneously has better alkali resistance. In addition, in order to further improve the flame retardance of the fiber reinforced plastic composite material, a flame retardant after-finishing process is combined, the flame retardance of the fiber reinforced plastic composite material is further improved in a mode of impregnating a phosphorus-nitrogen flame retardant, and the obtained fiber reinforced plastic composite material has the characteristics of environmental friendliness, alkali resistance and high flame retardance, and has potential application value in the fields of automotive interiors and living leather.
Disclosure of Invention
The invention aims at the technical analysis and provides a preparation method of alkali-resistant flame-retardant superfine fiber synthetic leather base. The flame-retardant superfine fiber synthetic leather bass prepared by the method has excellent alkali resistance and flame retardance, and has potential application value in the fields of automotive interior materials and synthetic leather.
The technical scheme of the invention is as follows: a preparation method of alkali-resistant flame-retardant superfine fiber synthetic leather bass. The phosphorus-containing flame-retardant waterborne polyurethane with excellent alkali resistance is obtained by adding flame-retardant silicone oil, is applied to superfine fiber non-woven cloth through wet impregnation, and is subjected to alkali deweighting and acid washing to obtain the flame-retardant microfiber bass with excellent alkali resistance, and finally, the flame-retardant microfiber bass with excellent alkali resistance and flame retardant property is obtained by combining flame-retardant after-finishing.
The technical key points of the invention are as follows: through a large number of experiments on the addition amount of flame-retardant silicone oil, the addition amount of phosphorus-containing flame retardant, the concentration of phosphorus-nitrogen flame retardant and the like in an experimental scheme, and the regulation and control of key technological parameters in the wet impregnation process and the flame-retardant after-finishing process, the prepared microfiber bass has the characteristics of environmental protection, alkali resistance and high flame retardance, and has potential application value in the fields of automotive interior materials and synthetic leather.
The invention provides a preparation method of alkali-resistant flame-retardant superfine fiber synthetic leather bass, which comprises the following steps:
step one: synthesizing alkali-resistant flame-retardant waterborne polyurethane;
adding polyether polyol and a proper amount of antioxidant 1010, and vacuum dehydrating at 105 ℃ for 1h until no bubbles appear in the flask; cooling to 65 ℃, sequentially adding isocyanate and a proper amount of organic bismuth catalyst according to a certain proportion, heating to 90 ℃ and reacting for 2 hours to obtain a prepolymer; cooling to 65 ℃, sequentially adding 2, 2-dimethylolpropionic acid, flame-retardant silicone oil, 2-butyl-2-ethyl-1, 3-propanediol and slowly dropwise adding a reactive phosphorus-containing flame retardant into the prepolymer, heating to 70 ℃, performing chain extension reaction for 2 hours, and adding a proper amount of acetone in the reaction process to regulate the viscosity; cooling to 60 ℃, and continuously adding acetone to react for 2 hours at 60 ℃; cooling to 35 ℃, adding KH550 for crosslinking reaction, and adding triethylamine for neutralization reaction for 10min; dispersing for 30s at 3500r/min, adding deionized water for emulsification reaction, continuously stirring for 25min at 1800r/min, adding diethylenetriamine for post-chain extension reaction at 800r/min, and reacting for 5min; removing acetone for 2 hours at 60 ℃ while curing, and thus obtaining the alkali-resistant flame-retardant waterborne polyurethane.
Step two: preparing alkali-resistant flame-retardant aqueous polyurethane impregnating slurry;
and adding a proper amount of thickener into the synthesized flame-retardant waterborne polyurethane to adjust the viscosity to be proper, and fully stirring the mixture for later use.
Step three: wet impregnation is carried out to prepare alkali-resistant flame-retardant superfine fiber synthetic leather bass;
after the superfine fiber nonwoven fabric is dried, the superfine fiber nonwoven fabric is impregnated with flame-retardant waterborne polyurethane, and a certain liquid carrying rate is ensured after padding; then rolling out excessive water after wet solidification process, and drying to constant weight; drying and then placing the dried product in sodium hydroxide solution with a certain concentration for a decrement process; and after the decrement, cleaning, and drying after an acid washing process to obtain the alkali-resistant flame-retardant microfiber bass.
Step four: the flame retardant after-finishing process improves the flame retardance of the microfiber bass;
adding a phosphorus-nitrogen flame retardant with a certain concentration in an impregnation mode to apply the phosphorus-nitrogen flame retardant to the alkali-resistant flame-retardant microfiber bass, rolling out excessive moisture to ensure a certain liquid carrying rate, and obtaining the microfiber bass with better alkali resistance and flame retardance.
The invention at least comprises the following beneficial effects:
according to the invention, the alkali resistance of the phosphorus-containing flame-retardant waterborne polyurethane is improved by introducing the flame-retardant silicone oil, and the flame-retardant microfiber base prepared by taking the flame-retardant waterborne polyurethane as the impregnating slurry has better alkali resistance, so that the requirement of a reduction process can be met; and simultaneously, the flame retardance of the superfine fiber synthetic leather bass is further improved by combining a flame retardant after-finishing process and a mode of impregnating the phosphorus-nitrogen flame retardant. The superfine fiber synthetic leather base with better flame retardance and alkali resistance can be obtained while the environment-friendly requirement is met, and the preparation process is simple, so that the requirement of mass production can be met, and the superfine fiber synthetic leather base has potential application value in the fields of automotive interiors and living leather.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Drawings
FIG. 1 is a graph showing test data of weight loss rate of flame retardant waterborne polyurethane (alkali resistance) and bass loss rate of ultrafine fiber synthetic leather according to the invention.
FIG. 2 is performance test data of a microfiber synthetic leather base of the present invention;
fig. 3 is a flow chart of an application embodiment of the present invention.
Detailed Description
The subject matter described herein will now be discussed with reference to example embodiments. It should be appreciated that these embodiments are discussed so that those skilled in the art will better understand and realize the subject matter described herein. Changes may be made in the function and arrangement of elements discussed without departing from the scope of the disclosure as set forth in the specification. Various examples may omit, replace, or add various procedures or components as desired. In addition, features described with respect to some examples may be combined in other examples as well.
Example 1:
the preparation method of the alkali-resistant flame-retardant superfine fiber synthetic leather bass comprises the following preparation steps:
step one: synthesizing alkali-resistant flame-retardant waterborne polyurethane;
61.05g of polypropylene glycol, 122.1g of polytetrahydrofuran ether glycol and 1.83g of antioxidant 1010 are added, and the mixture is dehydrated in vacuum for 1 hour at 105 ℃ until no bubbles appear in the flask; cooling to 65 ℃, adding 10.8g of hexamethylene diisocyanate, 55.08g of isophorone diisocyanate and 0.8g of organic bismuth catalyst, heating to 90 ℃ and reacting for 2 hours to obtain a prepolymer; cooling to 65 ℃, sequentially adding 9.6g of 2, 2-dimethylolpropionic acid, 14.85g of flame-retardant silicone oil, 2.9g of 2-butyl-2-ethyl-1, 3-propanediol and 11.8g of reactive phosphorus-containing flame retardant into the prepolymer, heating to 70 ℃, carrying out chain extension reaction for 2 hours, and adding a proper amount of acetone to regulate viscosity in the reaction process; cooling to 60 ℃, and continuously adding acetone to react for 2 hours at 60 ℃; cooling to 35 ℃, adding 1.73g of KH550 for crosslinking reaction, and adding 5.07g of triethylamine for neutralization reaction for 10min; dispersing for 30s at 3500r/min, adding 688.28g deionized water for emulsification reaction, continuously stirring for 25min at 1800r/min, adding 3.99g diethylenetriamine for post-chain extension reaction at 800r/min, and reacting for 5min; removing acetone for 2 hours at 60 ℃ while curing, and thus obtaining the alkali-resistant flame-retardant waterborne polyurethane.
Step two: preparing alkali-resistant flame-retardant aqueous polyurethane impregnating slurry;
and adding a proper amount of thickener into the synthesized flame-retardant waterborne polyurethane to adjust the viscosity to be proper, and fully stirring the mixture for later use.
Step three: wet impregnation is carried out to prepare alkali-resistant flame-retardant superfine fiber synthetic leather bass;
after the superfine fiber nonwoven fabric is dried, the superfine fiber nonwoven fabric is impregnated with flame-retardant waterborne polyurethane, and a certain liquid carrying rate is ensured after padding; then rolling out excessive water after wet solidification process, and drying to constant weight; drying and then placing the dried product in sodium hydroxide solution with a certain concentration for a decrement process; and after the decrement, cleaning, and drying after an acid washing process to obtain the alkali-resistant flame-retardant microfiber bass.
Example 2:
the preparation method of the alkali-resistant flame-retardant superfine fiber synthetic leather bass comprises the following preparation steps:
step one: synthesizing alkali-resistant flame-retardant waterborne polyurethane;
61.05g of polypropylene glycol, 122.1g of polytetrahydrofuran ether glycol and 1.83g of antioxidant 1010 are added, and the mixture is dehydrated in vacuum for 1 hour at 105 ℃ until no bubbles appear in the flask; cooling to 65 ℃, adding 10.8g of hexamethylene diisocyanate, 55.08g of isophorone diisocyanate and 0.8g of organic bismuth catalyst, heating to 90 ℃ and reacting for 2 hours to obtain a prepolymer; cooling to 65 ℃, sequentially adding 9.6g of 2, 2-dimethylolpropionic acid, 14.85g of flame-retardant silicone oil, 2.9g of 2-butyl-2-ethyl-1, 3-propanediol and 11.8g of reactive phosphorus-containing flame retardant into the prepolymer, heating to 70 ℃, carrying out chain extension reaction for 2 hours, and adding a proper amount of acetone to regulate viscosity in the reaction process; cooling to 60 ℃, and continuously adding acetone to react for 2 hours at 60 ℃; cooling to 35 ℃, adding 1.73g of KH550 for crosslinking reaction, and adding 5.07g of triethylamine for neutralization reaction for 10min; dispersing for 30s at 3500r/min, adding 688.28g deionized water for emulsification reaction, continuously stirring for 25min at 1800r/min, adding 3.99g diethylenetriamine for post-chain extension reaction at 800r/min, and reacting for 5min; removing acetone for 2 hours at 60 ℃ while curing, and thus obtaining the alkali-resistant flame-retardant waterborne polyurethane.
Step two: preparing alkali-resistant flame-retardant aqueous polyurethane impregnating slurry:
and adding a proper amount of thickener into the synthesized flame-retardant waterborne polyurethane to adjust the viscosity to be proper, and fully stirring the mixture for later use.
Step three: wet impregnation is carried out to prepare alkali-resistant flame-retardant superfine fiber synthetic leather bass;
after the superfine fiber nonwoven fabric is dried, the superfine fiber nonwoven fabric is impregnated with flame-retardant waterborne polyurethane, and a certain liquid carrying rate is ensured after padding; then rolling out excessive water after wet solidification process, and drying to constant weight; drying and then placing the dried product in sodium hydroxide solution with a certain concentration for a decrement process; and after the decrement, cleaning, and drying after an acid washing process to obtain the alkali-resistant flame-retardant microfiber bass.
Step four: the flame retardant after-finishing process improves the flame retardance of the microfiber bass;
the phosphorus-nitrogen flame retardant ZW370 with the mass fraction of 40% is applied to the alkali-resistant flame-retardant microfiber bass in an impregnation mode, excessive moisture is rolled out to ensure a certain liquid carrying rate, and the microfiber bass with better alkali resistance and flame retardance can be obtained.
Comparative example:
the preparation method of the alkali-resistant superfine fiber synthetic leather bass comprises the following preparation steps:
step one: synthesizing waterborne polyurethane;
66g of polypropylene glycol, 132g of polytetrahydrofuran ether glycol and 1.98g of antioxidant 1010 are added, and the mixture is dehydrated for 1 hour under vacuum at 105 ℃ until no bubbles appear in the flask; cooling to 65 ℃, adding 8.6g of hexamethylene diisocyanate, 43.86g of isophorone diisocyanate and 0.8g of organic bismuth catalyst, heating to 90 ℃ and reacting for 2 hours to obtain a prepolymer; cooling to 65 ℃, sequentially adding 9.6g of 2, 2-dimethylolpropionic acid and 2.9g of 2-butyl-2-ethyl-1, 3-propanediol into the prepolymer, heating to 70 ℃, performing chain extension reaction for 2 hours, and adding a proper amount of acetone in the reaction process to regulate the viscosity; cooling to 60 ℃, and continuously adding acetone to react for 2 hours at 60 ℃; cooling to 35 ℃, adding 1.58g of KH550 for crosslinking reaction, and adding 5.07g of triethylamine for neutralization reaction for 10min; dispersing for 30s at 3500r/min, adding 629.08g deionized water for emulsification reaction, continuously stirring for 25min at a speed of 1800r/min, adding 3.07g diethylenetriamine for post-chain extension reaction at a speed of 800r/min, and reacting for 5min; removing acetone for 2 hours at 60 ℃ while curing, and thus obtaining the waterborne polyurethane.
Step two: preparing aqueous polyurethane impregnating slurry;
and adding a proper amount of thickener into the synthesized aqueous polyurethane, adjusting the viscosity to be proper, and fully stirring the aqueous polyurethane for later use.
Step three: wet impregnation is carried out to prepare superfine fiber synthetic leather bass;
after the superfine fiber nonwoven fabric is dried, the superfine fiber nonwoven fabric contains water-impregnated polyurethane, and a certain liquid carrying rate is ensured after padding; then rolling out excessive water after wet solidification process, and drying to constant weight; drying and then placing the dried product in sodium hydroxide solution with a certain concentration for a decrement process; and (5) washing after the decrement, and drying after the acid washing process to obtain the microfiber bass.
As can be seen from the table data in the attached figure 1, the weight reduction rate of the flame-retardant waterborne polyurethane prepared by the invention is obviously reduced through alkali resistance test, and the weight reduction rate is relatively close to 30% of the theoretical value after the flame-retardant waterborne polyurethane is applied to superfine fiber synthetic leather bass, and the alkali resistance can be obviously improved through comparison; the reactive phosphorus-containing flame retardant adopted in the experiment is polyester diol, so that the problem of insufficient alkali resistance of the common phosphorus-containing flame retardant exists, and the introduction of the flame-retardant silicone oil is proved to obviously improve the alkali resistance of the flame-retardant silicone oil. From fig. 2, it can be seen from comparison of the combustion performance of the microfiber bass of example 1 and the comparative example that the reactive phosphorus-containing flame retardant and the flame-retardant silicone oil are introduced into the flame-retardant waterborne polyurethane, so that the flame retardance can be improved to a certain extent, and the requirement of < 100mm/min in the horizontal combustion test standard can be met. As can be seen by comparing the flame retardant performance with that of example 2, the flame retardant performance can be improved by combining the flame retardant after-finishing phosphorus-nitrogen-impregnated flame retardant while introducing the flame retardant waterborne polyurethane into the microfiber nonwoven fabric, and other performances and the comparative examples are almost equal or slightly higher.
Although the embodiments of the present invention have been disclosed above, it is not limited to the use listed in the specification and the embodiments, it is fully applicable to various fields suitable for the present invention, and thus the present invention is not limited to the above examples. Those skilled in the art will appreciate that, in light of the principles of the present invention, modifications and adaptations can be made without departing from the scope of the invention.
Claims (9)
1. The preparation method of the alkali-resistant flame-retardant superfine fiber synthetic leather base is characterized by comprising the following steps of:
step one: synthesizing alkali-resistant flame-retardant waterborne polyurethane;
adding polyether polyol and a proper amount of antioxidant 1010, and vacuum dehydrating at 105 ℃ for 1h until no bubbles appear in the flask; cooling to 65 ℃, sequentially adding isocyanate and a proper amount of organic bismuth catalyst according to a certain proportion, heating to 90 ℃ and reacting for 2 hours to obtain a prepolymer; cooling to 65 ℃, sequentially adding 2, 2-dimethylolpropionic acid, flame-retardant silicone oil, 2-butyl-2-ethyl-1, 3-propanediol and slowly dropwise adding a reactive phosphorus-containing flame retardant into the prepolymer, heating to 70 ℃, performing chain extension reaction for 2 hours, and adding a proper amount of acetone in the reaction process to regulate the viscosity; cooling to 60 ℃, and continuously adding acetone to react for 2 hours at 60 ℃; cooling to 35 ℃, adding KH550 for crosslinking reaction, and adding triethylamine for neutralization reaction for 10min; dispersing for 30s at 3500r/min, adding deionized water for emulsification reaction, continuously stirring for 25min at 1800r/min, adding diethylenetriamine for post-chain extension reaction at 800r/min, and reacting for 5min; removing acetone for 2 hours at 60 ℃ while curing, and thus obtaining the alkali-resistant flame-retardant waterborne polyurethane.
Step two: preparing alkali-resistant flame-retardant aqueous polyurethane impregnating slurry;
and adding a proper amount of thickener into the synthesized flame-retardant waterborne polyurethane to adjust the viscosity to be proper, and fully stirring the mixture for later use.
Step three: wet impregnation is carried out to prepare alkali-resistant flame-retardant superfine fiber synthetic leather bass;
after the superfine fiber nonwoven fabric is dried, the superfine fiber nonwoven fabric is impregnated with flame-retardant waterborne polyurethane, and a certain liquid carrying rate is ensured after padding; then rolling out excessive water after wet solidification process, and drying to constant weight; drying and then placing the dried product in sodium hydroxide solution with a certain concentration for a decrement process; and after the decrement, cleaning, and drying after an acid washing process to obtain the alkali-resistant flame-retardant microfiber bass.
Step four: the flame retardant after-finishing process improves the flame retardance of the microfiber bass;
adding a certain concentration of flame retardant in an impregnation mode to apply the flame retardant to the alkali-resistant flame-retardant microfiber bass, and rolling out excessive water to ensure a certain liquid carrying rate, so that the microfiber bass with better alkali resistance and flame retardance can be obtained.
2. The method for preparing alkali-resistant flame-retardant superfine fiber synthetic leather base according to claim 1, wherein in the first step, the flame-retardant silicone oil is BL-620LV silicone oil prepared by Jining Baichuan chemical Co., ltd, and the addition amount of the flame-retardant silicone oil is 2-10% of the total amount.
3. The method for preparing alkali-resistant flame-retardant superfine fiber synthetic leather base according to claim 1, wherein in the first step, the reactive phosphorus-containing flame retardant is BY3010, and the addition amount of the reactive phosphorus-containing flame retardant is 1-4% of the total amount.
4. The method for preparing alkali-resistant flame-retardant superfine fiber synthetic leather base according to claim 1, wherein in the second step, the solid content of flame-retardant waterborne polyurethane is 30-35%, the r value is 1.40-1.45, and the viscosity is 1000-1100 mPa.s.
5. The method for preparing the alkali-resistant flame-retardant superfine fiber synthetic leather base, according to claim 1, wherein in the third step, the liquid carrying rate of the flame-retardant waterborne polyurethane is 170-230%.
6. The method for preparing alkali-resistant flame-retardant superfine fiber synthetic leather base according to claim 1, wherein in the third step, the wet solidification process is as follows: solidifying in 6% citric acid for 20-30 min.
7. The method for preparing alkali-resistant flame-retardant superfine fiber synthetic leather base according to claim 1, wherein in the third step, the decrement process is as follows: 1% sodium hydroxide is boiled in water at 100 ℃ for 1h. The pickling process comprises the following steps: 0.1% citric acid is boiled at 60deg.C for 30min.
8. The method for preparing the alkali-resistant flame-retardant superfine fiber synthetic leather base, according to claim 1, wherein in the fourth step, the phosphorus-nitrogen type flame retardant is one or a combination of ZW370 and ZD950, wherein the liquid carrying rate is 50-80%, and the adding concentration is 20-60%.
9. The method for preparing the alkali-resistant flame-retardant superfine fiber synthetic leather base is characterized in that in the third step and the fourth step, padding process conditions are as follows: the pressure is 0.1Mpa, and the vehicle speed is 35r/min; the temperature of all the drying processes is 120 ℃.
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