CN117126366A - Synthesis process of flame-retardant polyurethane and application of flame-retardant polyurethane in fabric finishing - Google Patents
Synthesis process of flame-retardant polyurethane and application of flame-retardant polyurethane in fabric finishing Download PDFInfo
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- CN117126366A CN117126366A CN202311240409.6A CN202311240409A CN117126366A CN 117126366 A CN117126366 A CN 117126366A CN 202311240409 A CN202311240409 A CN 202311240409A CN 117126366 A CN117126366 A CN 117126366A
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- Prior art keywords
- flame
- retardant polyurethane
- carboxyl
- flame retardant
- phosphite
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- 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 85
- 239000003063 flame retardant Substances 0.000 title claims abstract description 85
- 239000004814 polyurethane Substances 0.000 title claims abstract description 47
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 14
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 10
- 239000000675 fabric finishing Substances 0.000 title claims description 5
- 238000009962 finishing (textile) Methods 0.000 title claims description 5
- 239000004744 fabric Substances 0.000 claims abstract description 67
- 229920000728 polyester Polymers 0.000 claims abstract description 46
- 239000011527 polyurethane coating Substances 0.000 claims abstract description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 52
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 28
- 238000001035 drying Methods 0.000 claims description 27
- 239000000839 emulsion Substances 0.000 claims description 25
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- -1 bis (carboxyl-hydroxyl) phosphite Chemical compound 0.000 claims description 21
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- LOUPRKONTZGTKE-WZBLMQSHSA-N Quinine Chemical compound C([C@H]([C@H](C1)C=C)C2)C[N@@]1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-WZBLMQSHSA-N 0.000 claims description 18
- VCAFTIGPOYBOIC-UHFFFAOYSA-N phenyl dihydrogen phosphite Chemical compound OP(O)OC1=CC=CC=C1 VCAFTIGPOYBOIC-UHFFFAOYSA-N 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 18
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 14
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 13
- 239000003054 catalyst Substances 0.000 claims description 13
- 150000008301 phosphite esters Chemical class 0.000 claims description 13
- 229920000570 polyether Polymers 0.000 claims description 13
- 229920005862 polyol Polymers 0.000 claims description 13
- 150000003077 polyols Chemical class 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 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 description 11
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 10
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 claims description 10
- 235000001258 Cinchona calisaya Nutrition 0.000 claims description 9
- LOUPRKONTZGTKE-UHFFFAOYSA-N cinchonine Natural products C1C(C(C2)C=C)CCN2C1C(O)C1=CC=NC2=CC=C(OC)C=C21 LOUPRKONTZGTKE-UHFFFAOYSA-N 0.000 claims description 9
- 229960000948 quinine Drugs 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 claims description 9
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 7
- 241000790917 Dioxys <bee> Species 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000010025 steaming Methods 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims 5
- 238000007790 scraping Methods 0.000 claims 1
- 238000009988 textile finishing Methods 0.000 abstract description 6
- 238000002485 combustion reaction Methods 0.000 abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 abstract description 4
- 239000011593 sulfur Substances 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 abstract description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 18
- 238000002390 rotary evaporation Methods 0.000 description 15
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000004970 Chain extender Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000004382 Amylase Substances 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 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
- C08G18/28—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
-
- 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
- C08G18/3891—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus having sulfur 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
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
- C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
- D06M15/579—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them modified by compounds containing phosphorus
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D06M2101/32—Polyesters
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
- D06M2200/30—Flame or heat resistance, fire retardancy properties
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of textile finishing, and discloses a synthesis process of flame-retardant polyurethane and application of the flame-retardant polyurethane in textile finishing. The flame-retardant polyurethane coating contains a phosphate structure and sulfur flame-retardant elements, and promotes the formation of a carbon layer on the surface of the polyester fabric during combustion, thereby playing a role in flame retardance of condensed phase carbon formation, improving the limiting oxygen index of the fabric, improving the vertical combustion performance and enhancing the flame retardance of the polyester fabric.
Description
Technical Field
The invention relates to the technical field of textile finishing, in particular to a synthesis process of flame-retardant polyurethane and application of the flame-retardant polyurethane in textile finishing.
Background
The polyester fabric has the advantages of high modulus, high strength, good heat resistance and the like, is widely applied to products such as clothing, home textiles and the like, but is poor in wearing comfort due to low hydrophilicity, easy to burn and melt and has the phenomenon of melt dripping, secondary damage can be caused, and the use of the polyester fabric is limited. Therefore, a novel textile finishing agent needs to be developed and applied to fabrics such as polyester, and the hydrophilicity, wearing comfort and flame retardance of the fabrics such as polyester are improved.
Polyurethane is a high molecular compound with good elasticity, high chemical resistance and excellent heat preservation and insulation property, and is widely applied to the fields of paint coating, textile finishing agent and the like, and patent CN114673015B discloses a doctor blade coating method for coating flame-retardant polyurethane on polyester fabrics and adopting amylase for treatment to obtain flame-retardant coated polyester fabrics, so that the tearing strength of the polyurethane coated polyester fabrics is improved, the flame-retardant property of the coated fabrics is not affected, and the problem of poor hydrophilicity of polyester fabrics is not solved.
Disclosure of Invention
The invention solves the technical problems that: the finishing agent of the flame-retardant polyurethane is prepared, and the problems of low hydrophilicity and flame retardance of the traditional polyester and other fabric are solved.
The technical scheme of the invention is as follows:
a synthesis process of flame-retardant polyurethane comprises the following steps: adding dry dehydrated polyether polyol and toluene diisocyanate into a flask, reacting for 1-2 hours at 70-80 ℃ under the protection of nitrogen, reducing the temperature to 45-50 ℃, adding a bis (carboxyl-hydroxyl) phosphite flame retardant, dibutyltin dilaurate and an acetone solvent, continuing to react for 1-2 hours, adding water, heating, stirring and volatilizing to remove acetone, and obtaining the aqueous emulsion of carboxyl-containing flame-retardant polyurethane; the structural formula of the bis (carboxyl-hydroxyl) phosphite flame retardant is as follows:
further, the ratio of the substances is polyether polyol toluene diisocyanate bis (carboxyl-hydroxyl) phosphite flame retardant dibutyl tin dilaurate=1 g (0.38-0.45 g) (0.12-0.2 g (0.002-0.003 g).
Further, the synthesis process of the bis (carboxyl-hydroxyl) phosphite flame retardant comprises the following steps:
s1, adding 1, 4-dioxane, diethyl phosphite, 4-hydroxybenzaldehyde and a catalyst quinine into a flask, reacting for 18-36 hours at room temperature, removing a solvent by rotary evaporation, washing with diethyl ether, and drying to obtain the phenol phosphite ester intermediate 1.
S2, adding toluene solvent, phenol phosphite ester intermediate 1, epoxy chloropropane and tetrabutylammonium chloride serving as catalysts into a flask, reacting for 2-3 hours at the temperature of 70-90 ℃ under the protection of nitrogen, then adding aqueous solution of sodium hydroxide, continuing to react for 4-8 hours, cooling, steaming to remove toluene, filtering, washing filter cakes with water and acetone in sequence, and drying to obtain the bis-epoxy phosphite ester intermediate 2.
S3, adding an N, N-dimethylformamide solvent, a dioxy phosphite ester intermediate 2, thioglycollic acid and triethylamine into the flask, adding ethyl acetate and water after the reaction, oscillating, standing, layering, concentrating the extracted ethyl acetate solution by rotary evaporation, washing with acetone, and drying to obtain the bis (carboxyl-hydroxyl) phosphite ester flame retardant. The reaction route is as follows:
further, the proportion of each substance in the S1 is diethyl phosphite, 4-hydroxybenzaldehyde and quinine=1 g (0.9-1.2 g) and (0.1-0.13 g.
Further, the mass fraction of the aqueous solution of the sodium hydroxide in the step S2 is 40-60%; the proportion of each substance is phenol phosphite ester intermediate 1, epoxy chloropropane, tetrabutylammonium chloride and sodium hydroxide=1 g (6-10) mL (0.012-0.018) g (0.7-1) g.
Further, the proportion of each substance in S3 in S2 is that of a dioxy phosphite ester intermediate 2, thioglycollic acid and triethylamine=1 g (0.45-0.62 g) (0.018-0.026 g).
Further, the reaction in S3 in S2 is stirred at a temperature of 25-40 ℃ for 12-24h.
Further, the application of the flame-retardant polyurethane in the fabric finishing is characterized in that the polyester fabric is used as a base fabric, the base fabric is coated by adopting aqueous emulsion of the flame-retardant polyurethane containing carboxyl, and the hydrophilic polyester fabric containing the flame-retardant polyurethane coating is obtained by drying the base fabric at the temperature of 70-100 ℃ for 1-3 hours.
The invention has the technical effects that: the novel efficient synthesis strategy is adopted, diethyl phosphite, 4-hydroxybenzaldehyde, epichlorohydrin, thioglycollic acid and the like are used as reaction raw materials, and the novel functional monomer bis (carboxyl-hydroxyl) phosphite flame retardant is prepared, contains dihydroxyl, and is subjected to polymerization reaction with polyether polyol and toluene diisocyanate to obtain the aqueous emulsion of carboxyl-containing flame-retardant polyurethane.
The surface of the polyester fabric is finished by utilizing the aqueous emulsion of the carboxyl-containing flame-retardant polyurethane, and the aqueous flame-retardant polyurethane coating is formed on the surface of the polyester fabric after drying and curing, so that the water contact angle of the polyester fabric is reduced, and the hydrophilicity and wearing comfort are improved.
The flame-retardant polyurethane coating contains a phosphate structure and sulfur flame-retardant elements, and promotes the formation of a carbon layer on the surface of the polyester fabric during combustion, thereby playing a role in flame retardance of condensed phase carbon formation, improving the limiting oxygen index of the fabric, improving the vertical combustion performance and enhancing the flame retardance of the polyester fabric.
Detailed Description
For further understanding of the present invention, the technical aspects of the present invention will be clearly and fully described in connection with the following embodiments, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, 150mL of 1, 4-dioxane, 6g of diethyl phosphite, 6.5g of 4-hydroxybenzaldehyde and 0.6g of quinine as a catalyst are added into a flask to react for 18h at room temperature, the solvent is removed by rotary evaporation, and the mixture is washed by diethyl ether and dried to obtain the phenol phosphite ester intermediate 1.
S2, adding 50mL of toluene solvent, 10g of phenol phosphite ester intermediate 1, 100mL of epoxy chloropropane, 0.12g of tetrabutylammonium chloride catalyst into a flask, reacting for 2 hours at 80 ℃ under the protection of nitrogen, then adding 40% of aqueous solution containing 10g of sodium hydroxide by mass percent, continuing to react for 8 hours, cooling, removing toluene by rotary evaporation, filtering, washing a filter cake with water and acetone in sequence, and drying to obtain the bis-epoxy phosphite ester intermediate 2.
S3, adding an N, N-dimethylformamide solvent, 8g of a dioxy phosphite ester intermediate 2, 3.6g of thioglycollic acid and 0.14g of triethylamine into a flask, stirring at 30 ℃ for 18h, adding ethyl acetate and water, vibrating, standing, layering, concentrating the extracted ethyl acetate solution by rotary evaporation, washing with acetone, and drying to obtain the bis (carboxyl-hydroxyl) phosphite ester flame retardant.
S4, adding 50g of dry and dehydrated polyether polyol and 22.5g of toluene diisocyanate into a flask, reacting for 2 hours at the temperature of 75 ℃ under the protection of nitrogen, cooling to 50 ℃, adding 6g of bis (carboxyl-hydroxyl) phosphite flame retardant, 0.12g of dibutyltin dilaurate and 60mL of acetone solvent, continuing reacting for 2 hours, adding 100mL of water, heating, stirring and volatilizing to remove acetone, and thus obtaining the aqueous emulsion of carboxyl-containing flame-retardant polyurethane.
S5, using the polyester fabric as a base fabric, carrying out blade coating on the base fabric by adopting aqueous emulsion of flame-retardant polyurethane containing carboxyl, and drying at 70 ℃ for 3 hours to obtain the hydrophilic polyester fabric containing the flame-retardant polyurethane coating.
Example 2
S1, adding 1, 4-dioxane, 6g diethyl phosphite, 5.4g 4-hydroxybenzaldehyde and 0.6g catalyst quinine into a flask, reacting for 24 hours at room temperature, removing the solvent by rotary evaporation, washing with diethyl ether, and drying to obtain the phenol phosphite ester intermediate 1.
S2, adding 80mL of toluene solvent, 10g of phenol phosphite ester intermediate 1, 60mL of epoxy chloropropane, 0.18g of tetrabutylammonium chloride serving as a catalyst into a flask, reacting for 2 hours at the temperature of 90 ℃ under the protection of nitrogen, then adding 50% of aqueous solution containing 8g of sodium hydroxide by mass percent, continuing to react for 8 hours, cooling, removing toluene by rotary evaporation, filtering, washing a filter cake with water and acetone in sequence, and drying to obtain the bis-epoxy phosphite ester intermediate 2.
S3, adding an N, N-dimethylformamide solvent, 8g of a dioxy phosphite ester intermediate 2, 4.9g of thioglycollic acid and 0.21g of triethylamine into a flask, stirring at 30 ℃ for 18h, adding ethyl acetate and water, vibrating, standing, layering, concentrating the extracted ethyl acetate solution by rotary evaporation, washing with acetone, and drying to obtain the bis (carboxyl-hydroxyl) phosphite ester flame retardant.
S4, adding 50g of dry and dehydrated polyether polyol and 21g of toluene diisocyanate into a flask, reacting for 2 hours at 80 ℃ under the protection of nitrogen, cooling to 50 ℃, adding 7g of bis (carboxyl-hydroxyl) phosphite flame retardant, 0.1g of dibutyltin dilaurate and 80mL of acetone solvent, continuing to react for 1 hour, adding 100mL of water, heating, stirring and volatilizing to remove acetone, and thus obtaining the aqueous emulsion of carboxyl-containing flame-retardant polyurethane.
S5, using the polyester fabric as a base fabric, carrying out blade coating on the base fabric by adopting aqueous emulsion of flame-retardant polyurethane containing carboxyl, and drying at 100 ℃ for 1h to obtain the hydrophilic polyester fabric containing the flame-retardant polyurethane coating.
Example 3
S1, adding 1, 4-dioxane, 6g diethyl phosphite, 7.2g 4-hydroxybenzaldehyde and 0.78g catalyst quinine into a flask, reacting for 24 hours at room temperature, removing the solvent by rotary evaporation, washing with diethyl ether, and drying to obtain the phenol phosphite ester intermediate 1.
S2, adding 100mL of toluene solvent, 10g of phenol phosphite ester intermediate 1, 100mL of epoxy chloropropane, 0.18g of tetrabutylammonium chloride serving as a catalyst into a flask, reacting for 2 hours at 90 ℃ under the protection of nitrogen, then adding 40% of aqueous solution containing 10g of sodium hydroxide by mass percent, continuing to react for 8 hours, cooling, removing toluene by rotary evaporation, filtering, washing a filter cake with water and acetone in sequence, and drying to obtain the bis-epoxy phosphite ester intermediate 2.
S3, adding an N, N-dimethylformamide solvent, 8g of a dioxy phosphite ester intermediate 2, 4.2g of thioglycollic acid and 0.18g of triethylamine into a flask, stirring at 25 ℃ for 18h, adding ethyl acetate and water, vibrating, standing, layering, concentrating the extracted ethyl acetate solution by rotary evaporation, washing with acetone, and drying to obtain the bis (carboxyl-hydroxyl) phosphite ester flame retardant.
S4, adding 50g of dry and dehydrated polyether polyol and 20.3g of toluene diisocyanate into a flask, reacting for 2 hours at the temperature of 80 ℃ under the protection of nitrogen, cooling to 45 ℃, adding 8.5g of bis (carboxyl-hydroxyl) phosphite flame retardant, 0.12g of dibutyltin dilaurate and 80mL of acetone solvent, continuing to react for 2 hours, adding 100mL of water, heating, stirring and volatilizing to remove acetone, and thus obtaining the aqueous emulsion of carboxyl-containing flame-retardant polyurethane.
S5, using the polyester fabric as a base fabric, carrying out blade coating on the base fabric by adopting aqueous emulsion of flame-retardant polyurethane containing carboxyl, and drying at 80 ℃ for 3 hours to obtain the hydrophilic polyester fabric containing the flame-retardant polyurethane coating.
Example 4
S1, adding 1, 4-dioxane, 6g diethyl phosphite, 7.2g 4-hydroxybenzaldehyde and 0.78g catalyst quinine into a flask, reacting for 18 hours at room temperature, removing the solvent by rotary evaporation, washing with diethyl ether, and drying to obtain the phenol phosphite ester intermediate 1.
S2, adding 80mL of toluene solvent, 10g of phenol phosphite ester intermediate 1, 60mL of epoxy chloropropane, 0.18g of tetrabutylammonium chloride serving as a catalyst into a flask, reacting for 3 hours at 70 ℃ under the protection of nitrogen, then adding 50% of aqueous solution containing 8g of sodium hydroxide by mass percent, continuing to react for 6 hours, cooling, removing toluene by rotary evaporation, filtering, washing a filter cake with water and acetone in sequence, and drying to obtain the bis-epoxy phosphite ester intermediate 2.
S3, adding an N, N-dimethylformamide solvent, 8g of a dioxy phosphite ester intermediate 2, 4.9g of thioglycollic acid and 0.21g of triethylamine into a flask, stirring at 25 ℃ for 12 hours, adding ethyl acetate and water, vibrating, standing, layering, concentrating the extracted ethyl acetate solution by rotary evaporation, washing with acetone, and drying to obtain the bis (carboxyl-hydroxyl) phosphite ester flame retardant.
S4, adding 50g of dry and dehydrated polyether polyol and 19g of toluene diisocyanate into a flask, reacting for 1h at 75 ℃ under the protection of nitrogen, reducing the temperature to 50 ℃, adding 10g of bis (carboxyl-hydroxyl) phosphite flame retardant, 0.15g of dibutyltin dilaurate and 80mL of acetone solvent, continuing to react for 1h, adding 80mL of water, heating, stirring and volatilizing to remove acetone, and thus obtaining the aqueous emulsion of carboxyl-containing flame-retardant polyurethane.
S5, using the polyester fabric as a base fabric, carrying out blade coating on the base fabric by adopting aqueous emulsion of flame-retardant polyurethane containing carboxyl, and drying at 80 ℃ for 2 hours to obtain the hydrophilic polyester fabric containing the flame-retardant polyurethane coating.
Comparative example 1
S1, adding 50g of dry and dehydrated polyether polyol and 22.5g of toluene diisocyanate into a flask, reacting for 2 hours at the temperature of 75 ℃ under the protection of nitrogen, cooling to 50 ℃, adding 2.5g of 1, 4-butanediol, 0.12g of dibutyltin dilaurate and 60mL of acetone solvent, continuously reacting for 1 hour, adding 100mL of water, heating, stirring and volatilizing to remove acetone, and thus obtaining the aqueous emulsion of the carboxyl-containing flame-retardant polyurethane.
S2, using the polyester fabric as a base fabric, carrying out blade coating on the base fabric by adopting aqueous emulsion of flame-retardant polyurethane containing carboxyl, and drying at 70 ℃ for 3 hours to obtain the hydrophilic polyester fabric containing the flame-retardant polyurethane coating.
Comparative example 2
S1, adding 1, 4-dioxane, 6g diethyl phosphite, 5.4g 4-hydroxybenzaldehyde and 0.65g catalyst quinine into a flask, reacting for 36h at room temperature, removing the solvent by rotary evaporation, washing with diethyl ether, and drying to obtain the phenol phosphite ester intermediate 1.
S4, adding 50g of dry and dehydrated polyether polyol and 22.5g of toluene diisocyanate into a flask, reacting for 2 hours at the temperature of 75 ℃ under the protection of nitrogen, reducing the temperature to 50 ℃, adding 6g of phenol phosphite ester intermediate 1, 0.12g of dibutyltin dilaurate and 60mL of acetone solvent, continuing to react for 2 hours, adding 100mL of water, heating, stirring, volatilizing to remove acetone, and obtaining the aqueous emulsion of the carboxyl-containing flame-retardant polyurethane.
S5, using the polyester fabric as a base fabric, carrying out blade coating on the base fabric by adopting aqueous emulsion of flame-retardant polyurethane containing carboxyl, and drying at 70 ℃ for 3 hours to obtain the polyester fabric containing the flame-retardant polyurethane coating.
The water contact angle of the polyester fabric is tested by adopting an optical contact angle tester.
The polyester fabric was soaked and washed in water, dried, repeated 20 times, and tested for water contact angle.
In each embodiment, the bis (carboxyl-hydroxyl) phosphite flame retardant is taken as a functional monomer, and is copolymerized with polyether polyol and toluene diisocyanate to obtain aqueous emulsion of carboxyl-containing flame-retardant polyurethane, the polyester fabric is finished, a hydrophilic polyurethane coating is formed on the surface of the polyester fabric, and the water contact angle and the hydrophilicity of the polyester fabric are improved.
Comparative example 1 an emulsion of polyurethane was obtained using 1, 4-butanediol as a chain extender; in comparative example 2, the phenol phosphite ester intermediate 1 is used as a functional monomer, so that the aqueous emulsion of the flame-retardant polyurethane containing carboxyl is obtained, the aqueous emulsion does not contain hydrophilic carboxyl, and the water contact angle of the polyester fabric is not improved when the polyester fabric is finished.
The flame retardant property of the polyester fabric adopts an oxygen index tester and a fabric flame retardant property tester.
In each embodiment, the bis (carboxyl-hydroxyl) phosphite flame retardant is taken as a functional monomer, and is copolymerized with polyether polyol and toluene diisocyanate to obtain aqueous emulsion of carboxyl-containing flame-retardant polyurethane, the polyester fabric is finished, and a polyurethane coating containing phosphate and sulfur flame-retardant elements is formed on the surface of the polyester fabric, so that the limiting oxygen index of the polyester fabric is improved, the vertical combustion performance is improved, and the flame retardance of the polyester fabric is enhanced.
In the comparative example 1, 4-butanediol is used as a chain extender to obtain polyurethane emulsion, which does not contain flame-retardant phosphate and sulfur elements and does not improve the flame retardant property of the polyester fabric.
Comparative example 2 the aqueous emulsion of flame-retardant polyurethane containing carboxyl is obtained by taking the intermediate 1 containing the phenol phosphite ester as a functional monomer, and the flame-retardant property of the polyester fabric is improved.
It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (9)
1. The synthesis process of the flame-retardant polyurethane is characterized by comprising the following steps of: adding dry dehydrated polyether polyol and toluene diisocyanate into a flask, reacting for 1-2 hours at 70-80 ℃ under the protection of nitrogen, reducing the temperature to 45-50 ℃, adding a bis (carboxyl-hydroxyl) phosphite flame retardant, dibutyltin dilaurate and an acetone solvent, continuing to react for 1-2 hours, adding water, heating, stirring and volatilizing to remove acetone, and obtaining the aqueous emulsion of carboxyl-containing flame-retardant polyurethane; the structural formula of the bis (carboxyl-hydroxyl) phosphite flame retardant is as follows:
2. the process for synthesizing flame-retardant polyurethane according to claim 1, wherein the ratio of the substances is polyether polyol toluene diisocyanate bis (carboxyl-hydroxyl) phosphite flame retardant dibutyl tin dilaurate=1 g (0.38-0.45 g) (0.12-0.2 g) (0.002-0.003 g).
3. The process for synthesizing flame retardant polyurethane according to claim 1, wherein the process for synthesizing the bis (carboxyl-hydroxyl) phosphite flame retardant comprises the steps of:
s1, adding 1, 4-dioxane, diethyl phosphite, 4-hydroxybenzaldehyde and a catalyst quinine into a flask, reacting for 18-36 hours at room temperature, steaming, washing and drying to obtain a phenol phosphite ester intermediate 1;
s2, adding toluene solvent, phenol phosphite ester intermediate 1, epoxy chloropropane and catalyst tetrabutylammonium chloride into a flask, reacting for 2-3 hours at 70-90 ℃ under the protection of nitrogen, then adding aqueous solution of sodium hydroxide, continuing to react for 4-8 hours, cooling, rotary steaming, filtering, washing and drying to obtain bis-epoxy phosphite ester intermediate 2;
s3, adding an N, N-dimethylformamide solvent, a dioxy phosphite ester intermediate 2, thioglycollic acid and triethylamine into the flask, extracting, steaming, washing and drying to obtain the bis (carboxyl-hydroxyl) phosphite ester flame retardant.
4. The process for synthesizing flame-retardant polyurethane according to claim 3, wherein the proportion of each substance in S1 is diethyl phosphite, 4-hydroxybenzaldehyde, quinine=1 g (0.9-1.2 g) and (0.1-0.13 g.
5. The process for synthesizing flame-retardant polyurethane according to claim 3, wherein the mass fraction of the aqueous solution of sodium hydroxide in S2 is 40-60%; the proportion of each substance is phenol phosphite ester intermediate 1, epoxy chloropropane, tetrabutylammonium chloride and sodium hydroxide=1 g (6-10) mL (0.012-0.018) g (0.7-1) g.
6. A process for the synthesis of flame retardant polyurethanes according to claim 3, wherein the ratio of the substances in S3 in S2 is that of the dioxyphosphite intermediate 2, thioglycollic acid and triethylamine = 1g (0.45-0.62) g (0.018-0.026) g.
7. A process for the synthesis of flame retardant polyurethane according to claim 3, wherein the reaction in S3 in S2 is stirred at a temperature of 25-40 ℃ for 12-24h.
8. Use of a flame retardant polyurethane according to any of claims 1 to 7 in fabric finishing.
9. The use of flame retardant polyurethane in fabric finishing according to claim 7, wherein the polyester fabric is used as a base fabric, the base fabric is coated by scraping with an aqueous emulsion of the flame retardant polyurethane containing carboxyl groups, and the hydrophilic polyester fabric containing the flame retardant polyurethane coating is obtained by drying at 70-100 ℃ for 1-3 hours.
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