CN105399921A - High solid content flame retardant wet-method foaming polyurethane used for synthetic leather and preparation method and application thereof - Google Patents
High solid content flame retardant wet-method foaming polyurethane used for synthetic leather and preparation method and application thereof Download PDFInfo
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- CN105399921A CN105399921A CN201510977020.9A CN201510977020A CN105399921A CN 105399921 A CN105399921 A CN 105399921A CN 201510977020 A CN201510977020 A CN 201510977020A CN 105399921 A CN105399921 A CN 105399921A
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- synthetic leather
- fire
- polyurathamc
- flame retardant
- flame
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- 238000000034 method Methods 0.000 claims abstract 20
- 239000003063 flame retardant Substances 0.000 claims abstract 12
- 229920005862 polyol Polymers 0.000 claims abstract 11
- 239000002649 leather substitute Substances 0.000 claims abstract 10
- 150000003077 polyols Chemical class 0.000 claims abstract 9
- 238000006243 chemical reaction Methods 0.000 claims abstract 6
- 239000004744 fabric Substances 0.000 claims abstract 4
- 238000002360 preparation method Methods 0.000 claims abstract 4
- -1 flame retardant polyol Chemical class 0.000 claims abstract 3
- 239000010985 leather Substances 0.000 claims abstract 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000003054 catalyst Substances 0.000 claims abstract 2
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract 2
- 239000011574 phosphorus Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 6
- 239000000203 mixture Substances 0.000 claims 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 4
- 150000002148 esters Chemical class 0.000 claims 4
- 239000008393 encapsulating agent Substances 0.000 claims 3
- 239000000835 fiber Substances 0.000 claims 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 2
- 125000001931 aliphatic group Chemical group 0.000 claims 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 2
- 238000005470 impregnation Methods 0.000 claims 2
- 238000009413 insulation Methods 0.000 claims 2
- 239000007788 liquid Substances 0.000 claims 2
- 239000004745 nonwoven fabric Substances 0.000 claims 2
- 150000003384 small molecules Chemical class 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- UZDJBTWIMFRARW-UHFFFAOYSA-N 2-[dimethoxyphosphorylmethyl(2-hydroxyethyl)amino]ethanol Chemical compound COP(=O)(OC)CN(CCO)CCO UZDJBTWIMFRARW-UHFFFAOYSA-N 0.000 claims 1
- 239000004135 Bone phosphate Substances 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims 1
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 101100184046 Schizosaccharomyces pombe (strain 972 / ATCC 24843) mid1 gene Proteins 0.000 claims 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 claims 1
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 229910052797 bismuth Inorganic materials 0.000 claims 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 claims 1
- 238000004043 dyeing Methods 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 claims 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 238000007654 immersion Methods 0.000 claims 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims 1
- 150000003951 lactams Chemical class 0.000 claims 1
- 150000002923 oximes Chemical class 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 claims 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract 5
- 229920001410 Microfiber Polymers 0.000 abstract 4
- 238000005187 foaming Methods 0.000 abstract 4
- 239000003658 microfiber Substances 0.000 abstract 4
- 229920002635 polyurethane Polymers 0.000 abstract 4
- 239000004814 polyurethane Substances 0.000 abstract 4
- 239000007787 solid Substances 0.000 abstract 4
- 239000012948 isocyanate Substances 0.000 abstract 1
- 150000002513 isocyanates Chemical class 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000007789 sealing Methods 0.000 abstract 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3882—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having phosphorus bound to oxygen only
- C08G18/3887—Phosphite compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
- C08G18/3889—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having nitrogen in addition to phosphorus
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
- D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
- D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2205/00—Condition, form or state of the materials
- D06N2205/04—Foam
- D06N2205/045—Froth
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
- D06N2209/00—Properties of the materials
- D06N2209/06—Properties of the materials having thermal properties
- D06N2209/067—Flame resistant, fire resistant
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
The present invention discloses high solid content flame retardant wet-method foaming polyurethane used for synthetic leather and a preparation method and application thereof, the preparation method of the high solid content flame retardant wet-method foaming polyurethane used for the synthetic leather comprises the following steps: a polyol, a flame retardant polyol and DMF are mixed and added in to isocyanate and a catalyst for reaction, then a sealing agent is added for reaction to obtain the high solid content flame retardant wet-method foaming polyurethane used for the synthetic leather, and the flame retardant polyol is one or a plurality of phosphorus-containing polyols. The high solid content flame retardant wet-method foaming polyurethane used for the synthetic leather can be used to prepare microfiber synthetic leather, the cost is reduced, operation is easy, pollution is reduced, microfiber base cloth hand feeling can be improved, microfiber base cloth flame retardance can be improved, and influences of a traditional flame retardant material addition method on other properties of the microfiber leather can be effectively overcome.
Description
Technical field
The present invention relates to a kind of fire-retardant wet method polyurathamc, and its preparation method and application.
Background technology
Superfine fiber polyurethane leather is the high-grade leatheroid of one grown up recent years, it is formed primarily of sea island fiber and urethane two portions, wherein polyurethane portion is by being impregnated into by polyurethane slurry in the non-woven that is processed into by sea island fiber, effectively be impregnated in non-woven for making polyurethane slurry, with a large amount of DMF solvents (more than 80%), urethane resin need be diluted, the course of processing can cause the solvent contamination of DMF, along with the further reinforcement of environmental protection policy, this method is more and more challenged aborning.Although there is document (patent CN103087285A) to propose to adopt solvent-free wet polyurethane technology, accomplish zero DMF solvent in process of production, break away from solvent contamination problem to a certain extent, but effectively foam due to urethane can not be realized after dipping, the actual superfine fiber fabric obtained of this solvent-free technology hardens, and has a strong impact on feel.
In recent years along with superfine fiber chemical leather is popularized, superfine fiber chemical leather in some new high-end fields such as automobile, electronics, space flight etc. also favored, simultaneously such high-end field it is also proposed new performance requriements to superfine fiber chemical leather.Especially quite harsh to the flame retardant properties of superfine fiber chemical leather in the field such as automotive trim, high-grade household.Traditional method in spinning process, adds nylon flame-retardant color master batch grain (CN101929083A) or add additional fire retardant (CN201310689458 to polyurethane slurry in steeping process, CN201510510077), but because the consistency of fire-retardant filler and nylon and urethane is all poor, the fire retardant being difficult to a type has flame retardant effect to nylon and urethane simultaneously, although and introduce the fire-retardant index that two or more fire retardants improves superfine fiber fabric to a certain extent simultaneously, but so a large amount of interpolation fire-retardant fillers is easy to separate out in following process or use procedure, have a strong impact on other performances of superfiber leather.
Summary of the invention
The object of this invention is to provide the fire-retardant wet method polyurathamc of a kind of use for synthetic leather large arch dam and preparation method and application, to solve the problems of the technologies described above.
The preparation of the fire-retardant wet method polyurathamc of use for synthetic leather large arch dam of the present invention, comprises the steps:
By polyvalent alcohol, flame-proof polyol, DMF mixing, add isocyanic ester and catalyzer, insulation reaction 2 ~ 8 hours at 70 ~ 80 DEG C, obtain the performed polymer that molecule chain end is isocyanic ester, then encapsulant is added, and 80 ~ 90 DEG C of insulation reaction 1 ~ 2 hour, namely obtain the fire-retardant wet method polyurathamc of described use for synthetic leather large arch dam;
The parts by weight of each component are:
Polyvalent alcohol 20 ~ 60 parts, flame-proof polyol 10 ~ 30 parts, DMF1 ~ 20 part, catalyzer 0.1 ~ 0.5 part;
The mol ratio (R value) of the total hydroxyl in the isocyanate group in described isocyanic ester and polyvalent alcohol and flame-proof polyol is 1.2 ~ 4.0;
Described polyvalent alcohol is the mixture of one or more arbitrary proportions in polyether Glycols, polyether-tribasic alcohol, polyester glycol, aliphatics small molecules glycol, aliphatics small molecules triol;
Described flame-proof polyol is one or more of phosphorus-containing polyol, such as: three (dipropylene glycol) phosphorous acid ester, N, the mixture of one or more arbitrary proportions in N-bis-(2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester, N, N-bis-(2-hydroxyethyl) aminomethylphosphonic acid dimethyl ester.
Described isocyanic ester is the mixture of one or more arbitrary proportions in tolylene diisocyanate, MDI, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenation 4,4-'-diphenylmethane diisocyanate.
Described catalyzer is the one in stannous octoate, dibutyl tin laurate, organic bismuth catalyst (such as: BiCAT8118).
Described encapsulant is the mixture of one or more arbitrary proportions in phenols, oximes, lactams.
The fire-retardant wet method polyurathamc of described use for synthetic leather large arch dam can be used for preparing superfine fiber chemical leather, and application method, comprises the steps:
(1) by fire-retardant for described use for synthetic leather large arch dam wet method polyurathamc, mix with solidifying agent and other auxiliary agents, obtain urethane containing immersion liquid;
The parts by weight of component are:
The fire-retardant wet method polyurathamc of use for synthetic leather large arch dam 100 parts
1 ~ 15 part, solidifying agent
Other auxiliary agents 1 ~ 30 part
Described solidifying agent is the mixture of one or more arbitrary proportions of aromatic diamine or aliphatie diamine.
Other described auxiliary agents comprise foam stabilizer, whipping agent, wetting agent, filler etc.;
Described foam stabilizer is selected from alkyl alcohol or aliphatic carboxylic acid.
Described whipping agent is expended microsphere powder, it is a kind of spherical particle of nucleocapsid structure, shell is the thermoplastic acrylic resin base polymer prepared for monomer with vinyl cyanide, methacrylonitrile etc., kernel is lower boiling alkane hydrocarbon, after heating, spherical particle volume can increase to self tens times by undergoes rapid expansion, can adopt commercially available prod, such as commodity are called the microballoon of EXPANCEL, or the expended microsphere powder product series that Japanese Matsumoto Yushi-Seiyaku Co., Ltd. produces.
Described wetting agent is selected from siliceous class wetting agent.
Described filler is selected from Microcrystalline Cellulose, light calcium carbonate or calcium sulfate.
(2) impregnation liquid is impregnated in islands-in-sea bicomponent fibre non-woven fabrics, by containing dipped non-woven fabrics, cross the DMF-aqueous solution and solidify, and 120 ~ 150 DEG C of oven dry, or without process of setting directly 120 ~ 150 DEG C of oven dry, namely obtain the polyurethane-base cloth of impregnation; Above-mentioned base cloth carried out decrement successively, dries, rub skin, split, mill skin, dyeing, the process such as veneer, namely obtain described superfine fiber chemical leather, this process is known method, as " synthetic leather technology " institute introduction method of Qu Jianbo chief editor.
The described weight concentration of solidifying the process DMF-aqueous solution is 30% ~ 50%, and temperature is 20 ~ 50 DEG C, and setting time is 1 ~ 10min.
Described islands-in-sea bicomponent fibre non-woven fabrics is nylon based islands-in-sea bicomponent fibre non-woven fabrics.
Compared with prior art, beneficial effect of the present invention is:
One, the amount of solid content of urethane resin prepared by the present invention, more than 80%, not only reduces the consumption of DMF in resin synthesis process, reduces costs, and in actual production process easy handling, effectively reduce the pollution of DMF to air; They are two years old, the present invention through the DMF-aqueous solution in drying course, the isocyanate group that solution is honored as a queen and solidifying agent and water react simultaneously and progressively solidify, in process, isocyanic ester and water react the carbon dioxide produced and can introduce foam structure in base cloth, improve the feel of super fine first fiber base cloth further; Three, the present invention by introducing the fire retardant of response type in polyurethane molecular chain backbone, not only increases the flame retardant properties of super fine base cloth, and effectively overcome tradition add fill out flame-proof material method on the impact of other performances of superfiber leather; Its four, the high solids content fire-retardant wet method polyurathamc of the present invention's synthesis is with low cost, and technique is simple, environmental protection.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be appreciated that, these embodiments only for illustrating the present invention, and are not intended to limit the scope of the invention.The improvement made according to the present invention of technician and adjustment, still belong to protection scope of the present invention in actual applications.Following examples are raw materials used be commercially available.
Embodiment 1
According to the mass fraction, the polyvalent alcohol of 20 parts, the phosphorus-containing polyol of 30 parts, the DMF of 1 part to be dropped in reactor and to stir, 50 parts of tolylene diisocyanates are dropped in 35 DEG C of downhill reaction stills, drip 0.1 part of stannous octoate, insulation reaction 2 hours at 70 DEG C, obtain the performed polymer that molecule chain end is isocyanic ester, finally add oximes encapsulant and 80 ~ 90 DEG C of insulation reaction 1 hour, namely obtain the fire-retardant wet method polyurathamc of high solids content.Wherein, the mol ratio (R value) of the hydroxyl in isocyanate group and polyvalent alcohol and flame-proof polyol is 1.2;
Described polyvalent alcohol is polyether glycol;
Described phosphorus-containing polyol adopts three (dipropylene glycol) phosphorous acid ester;
The method adopting the fire-retardant wet method polyurathamc of high solids content to prepare superfine fiber chemical leather is:
In the fire-retardant wet method polyurathamc of high solids content, add aromatic diamine curing agent and wetting agent, and stir, obtain urethane containing immersion liquid.
The parts by weight of component are:
The fire-retardant wet method polyurathamc of use for synthetic leather large arch dam 100 parts
1 part, solidifying agent
Wetting agent 1 part
Described wetting agent is the trade mark of YCK company is the siliceous class wetting agent of YCK-1010;
Be impregnated in islands-in-sea bicomponent fibre non-woven fabrics by repeatedly extruding by impregnation liquid, solidify process by doing containing dipped non-woven fabrics, wherein the weight concentration of the DMF-aqueous solution is 30%, temperature is 50 DEG C, setting time is 1min, and 120 DEG C of oven dry, namely obtain the polyurethane-base cloth of impregnation.Above-mentioned base cloth carried out decrement, dries, rub skin, split, mill skin, dyeing, the process such as veneer, namely obtain superfine fiber chemical leather.
Embodiment 2
According to the mass fraction, the polyvalent alcohol of 60 parts, the phosphorus-containing polyol of 10 parts, the DMF of 20 parts to be dropped in reactor and to stir, tolylene diisocyanate is dropped in 45 DEG C of downhill reaction stills, drip 0.5 part of stannous octoate, insulation reaction 3 hours at 80 DEG C, obtain the performed polymer that molecule chain end is isocyanic ester, finally add phenols encapsulant and 90 DEG C of insulation reaction 2 hours, namely obtain the fire-retardant wet method polyurathamc of high solids content.The mol ratio (R value) of the hydroxyl wherein in isocyanate group and polyvalent alcohol and flame-proof polyol is 4.0.
Described polyvalent alcohol is polyester glycol;
Described phosphorus-containing polyol adopts N, N-bis-(2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester;
The method adopting the fire-retardant wet method polyurathamc of high solids content to prepare superfine fiber chemical leather is:
In the fire-retardant wet method polyurathamc of high solids content, add aliphatics amine curing agent, wetting agent, foam stabilizer and filler, and stir, obtain urethane containing immersion liquid.
The parts by weight of component are:
Described foam stabilizer is selected from alkyl alcohol;
Described wetting agent is the trade mark of YCK company is the siliceous class wetting agent of YCK-1040;
Described filler is selected from Microcrystalline Cellulose;
Be impregnated in islands-in-sea bicomponent fibre non-woven fabrics by repeatedly extruding by impregnation liquid, solidify process by doing containing dipped non-woven fabrics, wherein the weight concentration of the DMF-aqueous solution is 50%, temperature is 20 DEG C, setting time is 10min, and 120 DEG C of oven dry, namely obtain the polyurethane-base cloth of impregnation.Above-mentioned base cloth carried out decrement, dries, rub skin, split, mill skin, dyeing, the process such as veneer, namely obtain superfine fiber chemical leather.
Embodiment 3
According to the mass fraction, the polyvalent alcohol of 50 parts, the Halogen polyvalent alcohol of 15 parts, the DMF of 10 parts to be dropped in reactor and to stir, MDI is dropped in 38 DEG C of downhill reaction stills, drip 0.3 part of dibutyl tin laurate, insulation reaction 4 hours at 73 DEG C, obtain the performed polymer that molecule chain end is isocyanic ester, finally add phenols encapsulant and 85 DEG C of insulation reaction 1.5 hours, namely obtain the fire-retardant wet method polyurathamc of high solids content.The mol ratio (R value) of the hydroxyl wherein in isocyanate group and polyvalent alcohol and flame-proof polyol is 3.0.
Described polyvalent alcohol is polyether triol;
Described phosphorus-containing polyol adopts N, N-bis-(2-hydroxyethyl) aminomethylphosphonic acid dimethyl ester;
The method adopting high solids content fire-retardant wet method polyurathamc to prepare superfine fiber chemical leather is: add aromatic amine solidifying agent, foam stabilizer, filler by fire-retardant for high solids content wet method polyurathamc, and stir, and obtains urethane containing immersion liquid.
The parts by weight of component are:
Described foam stabilizer is aliphatic carboxylic acid;
Described filler is selected from light calcium carbonate.
Be impregnated in islands-in-sea bicomponent fibre non-woven fabrics by repeatedly extruding by impregnation liquid, solidify process by doing containing dipped non-woven fabrics, wherein the weight concentration of the DMF-aqueous solution is 25%, temperature is 40 DEG C, setting time is 10min, and 130 DEG C of oven dry, namely obtain the polyurethane-base cloth of impregnation.Above-mentioned base cloth carried out decrement, dries, rub skin, split, mill skin, dyeing, the process such as veneer, namely obtain superfine fiber chemical leather.
Embodiment 4
According to the mass fraction, the polyvalent alcohol of 25 parts, the phosphorus-containing polyol of 17 parts, the DMF of 13 parts to be dropped in reactor and to stir, isophorone diisocyanate is dropped in 35 DEG C of downhill reaction stills, drip 0.5 part of BiCAT8118, insulation reaction 8 hours at 80 DEG C, obtain the performed polymer that molecule chain end is isocyanic ester, finally to add in lactams encapsulant and 90 DEG C of insulation reaction 2 hours, namely obtain the fire-retardant wet method polyurathamc of high solids content.The mol ratio (R value) of the hydroxyl wherein in isocyanate group and polyvalent alcohol and flame-proof polyol is 3.0.
Described polyvalent alcohol is polyether glycol and polyester glycol;
Described phosphorus-containing polyol adopts N, N-bis-(2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester;
The method adopting high solids content fire-retardant wet method polyurathamc to prepare superfine fiber chemical leather is: add aliphatics amine curing agent and whipping agent by fire-retardant for high solids content wet method polyurathamc, and stir, and obtains urethane containing immersion liquid.
The parts by weight of component are:
The fire-retardant wet method polyurathamc of use for synthetic leather large arch dam 100 parts
1 part, solidifying agent
Whipping agent 5 parts
Described whipping agent is selected from commodity and is called EXPANCEL microballoon.
By repeatedly extruding, impregnation liquid being impregnated in islands-in-sea bicomponent fibre non-woven fabrics, by containing the dipped direct 150 DEG C of oven dry of non-woven fabrics, namely obtaining the polyurethane-base cloth of impregnation.Above-mentioned base cloth carried out decrement, dries, rub skin, split, mill skin, dyeing, the process such as veneer, namely obtain superfine fiber chemical leather.
Embodiment 5
According to the mass fraction, the polyvalent alcohol of 20 parts, the phosphorus-containing polyol of 10 parts, the Halogen polyvalent alcohol of 10 parts, the DMF of 11 parts to be dropped in reactor and to stir, hydrogenation 4 is dropped in 45 DEG C of downhill reaction stills, 4-'-diphenylmethane diisocyanate, drip 5 parts of BiCAT8118, insulation reaction 8 hours at 80 DEG C, obtain the performed polymer that molecule chain end is isocyanic ester, finally add 2 parts of oximes encapsulants and 4 parts of lactams encapsulants, and 90 DEG C of insulation reaction 2 hours, namely obtain the fire-retardant wet method polyurathamc of high solids content.The mol ratio (R value) of the hydroxyl wherein in isocyanate group and polyvalent alcohol and flame-proof polyol is 1.8.
Described polyvalent alcohol is polyether glycol and small molecules triol;
Described phosphorus-containing polyol adopts N, N-bis-(2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester and N, N-bis-(2-hydroxyethyl) aminomethylphosphonic acid dimethyl ester.
The method adopting high solids content fire-retardant wet method polyurathamc to prepare superfine fiber chemical leather is: will add aliphatics amine and aromatic amine solidifying agent and whipping agent in fire-retardant for high solids content wet method polyurathamc, and stir, obtain urethane containing immersion liquid.
The parts by weight of component are:
The fire-retardant wet method polyurathamc of use for synthetic leather large arch dam 100 parts
15 parts, solidifying agent
Whipping agent 4 parts
The F-50D expended microsphere powder that whipping agent selects Japanese Matsumoto Yushi-Seiyaku Co., Ltd. to produce.
By repeatedly extruding, impregnation liquid being impregnated in islands-in-sea bicomponent fibre non-woven fabrics, by containing the dipped direct 120 DEG C of oven dry of non-woven fabrics, namely obtaining the polyurethane-base cloth of impregnation.Above-mentioned base cloth carried out decrement, dries, rub skin, split, mill skin, dyeing, the process such as veneer, namely obtain superfine fiber chemical leather.
Table one is listed in for the test of embodiment 1-5 resin solid content, flame retardant rating test and pliability test.Wherein flame retardant properties test is tested according to GB GB8410, and pliability test adopts High Speed Rail Testing Instruments company limited pliability tester (GT-303) to test.
Table 1
As known from Table 1, compare with no-solvent type superfiber leather with traditional solvent-borne type superfiber leather, superfiber leather prepared by the present invention has flame retardant properties and the pliability of relatively high amount of solid content and excellence.
Claims (10)
1. the preparation of the fire-retardant wet method polyurathamc of use for synthetic leather large arch dam, is characterized in that, comprise the steps:
By polyvalent alcohol, flame-proof polyol, DMF mixing, add isocyanic ester and part catalyzer, reaction, then encapsulant is added, reaction, namely obtains the fire-retardant wet method polyurathamc of described use for synthetic leather large arch dam, and described flame-proof polyol is one or more of phosphorus-containing polyol.
2. method according to claim 1, is characterized in that, the parts by weight of each component are: polyvalent alcohol 20 ~ 60 parts, flame-proof polyol 10 ~ 30 parts, DMF1 ~ 20 part, catalyzer 0.1 ~ 0.5 part; The mol ratio (R value) of the hydroxyl in the isocyanate group in described isocyanic ester and polyvalent alcohol and flame-proof polyol is 1.2 ~ 4.0.
3. method according to claim 1, is characterized in that, by polyvalent alcohol, flame-proof polyol, DMF mixing, add isocyanic ester and part catalyzer, at 70 ~ 80 DEG C, insulation reaction 2 ~ 8 hours, then adds encapsulant, and 80 ~ 90 DEG C of insulation reaction 1 ~ 2 hour.
4. method according to claim 1, is characterized in that, described polyvalent alcohol is the mixture of one or more arbitrary proportions in polyether Glycols, polyether-tribasic alcohol, polyester glycol, aliphatics small molecules glycol, aliphatics small molecules triol.
5. method according to claim 1, it is characterized in that, described isocyanic ester is the mixture of one or more arbitrary proportions in tolylene diisocyanate, MDI, isophorone diisocyanate, hexamethylene diisocyanate, hydrogenation 4,4-'-diphenylmethane diisocyanate.
6. method according to claim 1, it is characterized in that, described catalyzer is the one in stannous octoate, dibutyl tin laurate, organic bismuth catalyst, and described encapsulant is the mixture of one or more arbitrary proportions in phenols, oximes, lactams.
7. the method according to any one of claim 1 ~ 6, it is characterized in that, described flame-proof polyol is three (dipropylene glycol) phosphorous acid ester, N, the mixture of one or more arbitrary proportions in N-bis-(2-hydroxyethyl) aminomethy-lenephosphonic acids diethyl ester, N, N-bis-(2-hydroxyethyl) aminomethylphosphonic acid dimethyl ester.
8. the fire-retardant wet method polyurathamc of use for synthetic leather large arch dam that according to any one of claim 1 ~ 7 prepared by method.
9. the application of the fire-retardant wet method polyurathamc of use for synthetic leather large arch dam according to claim 8, is characterized in that, for the preparation of superfine fiber chemical leather.
10. application according to claim 9, is characterized in that, application method comprises the steps:
(1) by fire-retardant for described use for synthetic leather large arch dam wet method polyurathamc, mix with solidifying agent and other auxiliary agents, obtain urethane containing immersion liquid;
(2) impregnation liquid is impregnated in islands-in-sea bicomponent fibre non-woven fabrics, by containing dipped non-woven fabrics, cross the DMF-aqueous solution and solidify, and 120 ~ 150 DEG C of oven dry, or without process of setting directly 120 ~ 150 DEG C of oven dry, namely obtain the polyurethane-base cloth of impregnation; Above-mentioned base cloth carried out decrement successively, dries, rub skin, split, mill skin, dyeing, Overlaying process, namely obtain described superfine fiber chemical leather.
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