CN115160504B - Intrinsic flame-retardant polyurethane-acrylate emulsion and preparation method thereof - Google Patents
Intrinsic flame-retardant polyurethane-acrylate emulsion and preparation method thereof Download PDFInfo
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- CN115160504B CN115160504B CN202210796278.9A CN202210796278A CN115160504B CN 115160504 B CN115160504 B CN 115160504B CN 202210796278 A CN202210796278 A CN 202210796278A CN 115160504 B CN115160504 B CN 115160504B
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- acrylate
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- polyurethane
- flame retardant
- monomer
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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 79
- 239000000839 emulsion Substances 0.000 title claims abstract description 77
- 239000003063 flame retardant Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000004945 emulsification Methods 0.000 title description 8
- 239000000178 monomer Substances 0.000 claims abstract description 65
- 239000004814 polyurethane Substances 0.000 claims abstract description 48
- 229920002635 polyurethane Polymers 0.000 claims abstract description 46
- -1 papermaking Substances 0.000 claims abstract description 33
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims description 31
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 28
- 238000006116 polymerization reaction Methods 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000003112 inhibitor Substances 0.000 claims description 16
- 229920005862 polyol Polymers 0.000 claims description 16
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 15
- 125000005442 diisocyanate group Chemical group 0.000 claims description 14
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 14
- 239000003995 emulsifying agent Substances 0.000 claims description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 239000003999 initiator Substances 0.000 claims description 9
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 8
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 8
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 8
- 229920001610 polycaprolactone Polymers 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 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 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 7
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 6
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 6
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- JSPBAVGTJNAVBJ-UHFFFAOYSA-N ethyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCC)OC1=CC=CC=C1 JSPBAVGTJNAVBJ-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004632 polycaprolactone Substances 0.000 claims description 6
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 claims description 6
- 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 description 5
- 239000004970 Chain extender Substances 0.000 claims description 5
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 4
- CNCOEDDPFOAUMB-UHFFFAOYSA-N N-Methylolacrylamide Chemical compound OCNC(=O)C=C CNCOEDDPFOAUMB-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 4
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims description 4
- 238000005809 transesterification reaction Methods 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 3
- CHUGKEQJSLOLHL-UHFFFAOYSA-N 2,2-Bis(bromomethyl)propane-1,3-diol Chemical compound OCC(CO)(CBr)CBr CHUGKEQJSLOLHL-UHFFFAOYSA-N 0.000 claims description 3
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 claims description 3
- SPAUYKHQVLTCOL-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C SPAUYKHQVLTCOL-UHFFFAOYSA-N 0.000 claims description 3
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 150000005215 alkyl ethers Chemical class 0.000 claims description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 3
- MRVZORUPSXTRHD-UHFFFAOYSA-N bis(hydroxymethyl)phosphorylmethanol Chemical compound OCP(=O)(CO)CO MRVZORUPSXTRHD-UHFFFAOYSA-N 0.000 claims description 3
- XGZNHFPFJRZBBT-UHFFFAOYSA-N ethanol;titanium Chemical compound [Ti].CCO.CCO.CCO.CCO XGZNHFPFJRZBBT-UHFFFAOYSA-N 0.000 claims description 3
- 229950000688 phenothiazine Drugs 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium(IV) ethoxide Substances [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 3
- ADJMNWKZSCQHPS-UHFFFAOYSA-L zinc;6-methylheptanoate Chemical compound [Zn+2].CC(C)CCCCC([O-])=O.CC(C)CCCCC([O-])=O ADJMNWKZSCQHPS-UHFFFAOYSA-L 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 238000004806 packaging method and process Methods 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract description 3
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 150000003254 radicals Chemical class 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006386 neutralization reaction Methods 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009775 high-speed stirring Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- NKZQKINFDLZVRY-UHFFFAOYSA-N n-butylbutan-1-amine;toluene Chemical compound CC1=CC=CC=C1.CCCCNCCCC NKZQKINFDLZVRY-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 description 2
- SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- SXWZSWLBMCNOPC-UHFFFAOYSA-M potassium;6-methylheptanoate Chemical compound [K+].CC(C)CCCCC([O-])=O SXWZSWLBMCNOPC-UHFFFAOYSA-M 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 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 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of polyurethane, in particular to an intrinsic flame-retardant polyurethane-acrylate emulsion and a preparation method thereof. The invention adopts the means of molecular structure design, and prepares a novel phosphorus-containing flame retardant by introducing groups with flame retardant functions into acrylate monomers; and then synthesizing polyurethane emulsion with double bonds by adopting molecular design, and polymerizing the emulsion serving as seed emulsion with acrylate monomer free radical emulsion with flame retardant function to obtain the PUA dispersoid. The PUA emulsion with PU performance, PA performance and flame retardant performance is obtained by the invention, the synthesis process is simple, the flame retardant performance is better, and the PUA emulsion can be widely applied to the fields of textile, papermaking, coating, packaging and the like, and has great application prospect.
Description
Technical Field
The invention relates to the technical field of polyurethane, in particular to an intrinsic flame-retardant polyurethane-acrylate emulsion and a preparation method thereof.
Background
Currently, polyurethane materials have been widely used in various fields in life, and become an indispensable existence in life. However, the polyether structure on the molecular chain of polyurethane determines that polyurethane products are inflammable products, and LOI (limiting oxygen index) of polyurethane without flame retardant treatment is only 18%, so that fire hazard is caused to endanger human life and property safety. Therefore, the performance research on the flame retardance of the polyurethane material is of great significance.
Flame retardants are a class of flame retardants that improve the flame retardancy of flammable materials. The prior polyurethane materials are mostly added with halogen flame retardants, but the added amount is relatively large, the flame retardant performance is general, the added flame retardants are easy to migrate out of a polymer network along with the service time, the environment is polluted, and the mechanical performance and the flame retardant durability of the materials are reduced. Therefore, research on halogen-free intrinsic flame retardant technology is certainly an important direction in the future.
At present, the flame retardant is in compliance with the development trend of environmental protection and innocuity, and is applied to a large number of phosphorus flame retardants. The diphenyl ethyl phosphate is taken as a phosphorus-containing substance, has good flame retardant property, and is found by literature search, and no record of realizing the flame retardant property by using the diphenyl ethyl phosphate and acrylate composite modified polyurethane is disclosed at present.
Disclosure of Invention
In order to solve the problems, the invention aims to provide an intrinsic flame-retardant polyurethane-acrylate emulsion and a preparation method thereof. The invention adopts the means of molecular structure design, and prepares a novel phosphorus-containing flame retardant by introducing groups with flame retardant functions into acrylate monomers; and then synthesizing polyurethane emulsion with double bonds by adopting molecular design, and polymerizing the emulsion serving as seed emulsion with acrylate monomer free radical emulsion with flame retardant function to obtain the PUA dispersoid. The invention obtains the PUA emulsion with Polyurethane (PU) performance, polyamide (PA) performance and flame retardant performance, has simple synthesis process and better flame retardant performance, can be widely applied to the fields of textile, papermaking, coating, packaging and the like, and has great application prospect.
The aim of the invention can be achieved by the following technical scheme:
the first object of the invention is to provide an intrinsic flame-retardant polyurethane-acrylate emulsion, which is prepared by polymerization reaction of an acrylate monomer with flame-retardant function and a polyurethane emulsion containing double bonds;
the acrylate monomer with the flame-retardant function comprises the following raw material components in percentage by mass: 20-85% of monohydroxy acrylic ester monomer, 1-15% of flame-retardant functional monomer, 0.5-3% of catalyst and the balance of polymerization inhibitor;
the polyurethane emulsion comprises the following raw materials in percentage by mass: 10-40% of diisocyanate, 20-80% of oligomer polyol, 0.01-0.3% of dibutyltin dilaurate, 2.8-4.5% of dimethylolpropionic acid and 2.5-10% of chain extender.
The second object of the invention is to provide a preparation method of an intrinsic flame retardant polyurethane-acrylate emulsion, which comprises the following steps:
(1) Preparation of acrylate monomer with flame retardant property: uniformly mixing a monohydroxy acrylic ester monomer and a flame-retardant functional monomer, and then adding a catalyst and a polymerization inhibitor; after the transesterification reaction, an acrylic ester monomer with flame retardant property is obtained;
(2) Preparation of polyurethane emulsion: uniformly mixing diisocyanate, oligomer polyol and dimethylolpropionic acid, then adding a catalyst and a monohydroxy acrylic ester monomer, performing a prepolymerization reaction to obtain a prepolymer containing double bonds, and performing aftertreatment to obtain polyurethane emulsion;
(3) Preparation of an intrinsic flame retardant polyurethane-acrylate emulsion: and (3) taking the polyurethane emulsion prepared in the step (2) as seeds, and carrying out polymerization reaction with the acrylate monomer with the flame retardant function, the initiator and the emulsifier prepared in the step (1) to obtain the intrinsic flame retardant polyurethane-acrylate emulsion (PUA composite emulsion).
In one embodiment of the present invention, in the step (1), the monohydroxyacrylate monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate or hydroxypropyl acrylate;
the flame-retardant functional monomer is selected from one or more of diphenyl ethyl phosphate, triethyl phosphate, tributyl phosphate, toluene diphenyl phosphate, trimethylol phosphorus oxide, dibromo neopentyl glycol or DOPO-hydroquinone;
the catalyst is selected from one or more of p-toluenesulfonic acid, sodium methoxide, organic tin, zinc isooctanoate, tetraethyl titanate or tetrabutyl titanate;
the polymerization inhibitor is selected from one or more of hydroquinone monomethyl ether, hydroquinone, phenothiazine or nitroxide free radical polymerization inhibitors.
In one embodiment of the present invention, in step (1), the molar ratio of the monohydroxyacrylate monomer to the flame retardant functional monomer is 1.5:1 to 1:2.
in one embodiment of the invention, in step (1), the reaction temperature is 110-160 ℃ during the transesterification reaction; the reaction time is 6-10h.
In one embodiment of the invention, step (2), the molar ratio of diisocyanate, oligomer polyol, dimethylolpropionic acid and monohydroxyacrylate monomer is 9:3:1.5:0.8 to 6:3:1.5:0.9.
in one embodiment of the present invention, in step (2), the diisocyanate is selected from one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), diphenylmethane-4, 4-diisocyanate (MDI), 4-dicyclohexylmethane diisocyanate (H-MDI) or terephthalyl diisocyanate (PPDI);
the oligomer polyol is selected from one or more of polytetrahydrofuran ether glycol (PTMG), polycaprolactone glycol (PCL), polyethylene glycol (PEG), polypropylene glycol (PPG), polycarbonate glycol (PCDL), polyethylene glycol adipate glycol (PEA) or polybutylene adipate (PBA);
the catalyst is selected from one or more of dibutyl tin dilaurate, potassium isooctanoate, stannous octoate, organic bismuth, triethylamine, triethyldiamine or N, N-dimethyl cyclohexylamine;
the monohydroxy acrylic ester monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, glycidyl methacrylate or N-methylolacrylamide.
In one embodiment of the present invention, in step (2), the reaction temperature during the prepolymerization is 80 ℃; the reaction time was 4.5h.
In one embodiment of the invention, the post-treatment is neutralization, emulsification, post-chain extension.
In one embodiment of the invention, the neutralizing agent used in the neutralization process is triethylamine.
In one embodiment of the present invention, the chain extender used in the chain extension process is isophorone diamine.
In one embodiment of the invention, in the step (3), the mass ratio of the polyurethane emulsion, the acrylate monomer with flame retardant function, the initiator and the emulsifier is 50:10:1:1 to 50:3:0.3:0.2.
the initiator is one or more selected from ammonium persulfate, potassium persulfate, cumene hydroperoxide, tert-butyl hydroperoxide or benzoyl;
the emulsifier is selected from one or more of soaps, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyoxyethylene alkyl ether sulfate or polyoxyethylene alkyl ether.
In one embodiment of the present invention, in step (3), the reaction temperature during the polymerization reaction is 75 ℃; the reaction time was 3h.
In one embodiment of the invention, the polymerization process is under an inert atmosphere.
In one embodiment of the invention, the polymerization reaction is performed for 2 hours at a low temperature, the temperature is raised to 80 ℃, the temperature is kept for a period of time, and the temperature is reduced to 40-60 ℃ for discharging.
Compared with the prior art, the invention has the following beneficial effects:
the PUA emulsion with PU performance, PA performance and flame retardant performance is obtained by the invention, the synthesis process is simple, the flame retardant performance is better, and the PUA emulsion can be widely applied to the fields of textile, papermaking, coating, packaging and the like, and has great application prospect.
Detailed Description
The invention provides an intrinsic flame-retardant polyurethane-acrylate emulsion, which is prepared by polymerization reaction of an acrylate monomer with a flame-retardant function and a polyurethane emulsion containing double bonds;
the acrylate monomer with the flame-retardant function comprises the following raw material components in percentage by mass: 20-85% of monohydroxy acrylic ester monomer, 1-15% of flame-retardant functional monomer, 0.5-3% of catalyst and the balance of polymerization inhibitor;
the polyurethane emulsion comprises the following raw materials in percentage by mass: 10-40% of diisocyanate, 20-80% of polyol, 0.01-0.3% of dibutyltin dilaurate, 2.8-4.5% of dimethylolpropionic acid and 2.5-10% of chain extender.
The invention provides a preparation method of an intrinsic flame-retardant polyurethane-acrylate emulsion, which comprises the following steps:
(1) Preparation of acrylate monomer with flame retardant property: uniformly mixing a monohydroxy acrylic ester monomer and a flame-retardant functional monomer, and then adding a catalyst and a polymerization inhibitor; after the reaction, an acrylic ester monomer with flame retardant property is obtained;
(2) Preparation of polyurethane emulsion: uniformly mixing diisocyanate, oligomer polyol and dimethylolpropionic acid, then adding a catalyst and a monohydroxy acrylic ester monomer, reacting to obtain a prepolymer containing double bonds, and performing aftertreatment to obtain polyurethane emulsion;
(3) Preparation of an intrinsic flame retardant polyurethane-acrylate emulsion: and (3) taking the polyurethane emulsion prepared in the step (2) as seeds, and carrying out polymerization reaction with the acrylate monomer with the flame retardant function, the initiator and the emulsifier prepared in the step (1) to obtain the intrinsic flame retardant polyurethane-acrylate emulsion.
In one embodiment of the present invention, in the step (1), the monohydroxyacrylate monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, glycidyl methacrylate or N-methylolacrylamide;
the flame-retardant functional monomer is selected from one or more of diphenyl ethyl phosphate, triethyl phosphate, tributyl phosphate, toluene diphenyl phosphate, trimethylol phosphorus oxide, dibromo neopentyl glycol or DOPO-hydroquinone;
the catalyst is selected from one or more of p-toluenesulfonic acid, sodium methoxide, organic tin, zinc isooctanoate, tetraethyl titanate or tetrabutyl titanate;
the polymerization inhibitor is selected from one or more of hydroquinone monomethyl ether, hydroquinone, phenothiazine or nitroxide free radical polymerization inhibitors.
In one embodiment of the present invention, in step (1), the molar ratio of the monohydroxyacrylate monomer to the flame retardant functional monomer is 1.5:1 to 1:2.
in one embodiment of the invention, in step (1), the reaction temperature is 110-160 ℃ during the reaction; the reaction time is 6-10h.
In one embodiment of the invention, step (2), the molar ratio of diisocyanate, oligomer polyol, dimethylolpropionic acid and monohydroxyacrylate monomer is 9:3:1.5:0.8 to 6:3:1.5:0.9.
in one embodiment of the present invention, in step (2), the diisocyanate is selected from one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), toluene Diisocyanate (TDI), diphenylmethane-4, 4-diisocyanate (MDI), 4-dicyclohexylmethane diisocyanate (H-MDI) or terephthalyl diisocyanate (PPDI);
the oligomer polyol is selected from one or more of polytetrahydrofuran ether glycol (PTMG), polycaprolactone glycol (PCL), polyethylene glycol (PEG), polypropylene glycol (PPG), polycarbonate glycol (PCDL), polyethylene glycol adipate glycol (PEA) or polybutylene adipate (PBA);
the catalyst is selected from one or more of dibutyl tin dilaurate, potassium isooctanoate, stannous octoate, organic bismuth, triethylamine, triethyldiamine or N, N-dimethyl cyclohexylamine;
the monohydroxy acrylic ester monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, glycidyl methacrylate or N-methylolacrylamide.
In one embodiment of the invention, in step (2), the reaction temperature is 80 ℃ during the reaction; the reaction time was 4.5h.
In one embodiment of the invention, the post-treatment is neutralization, emulsification, post-chain extension.
In one embodiment of the invention, the neutralizing agent used in the neutralization process is triethylamine.
In one embodiment of the present invention, the chain extender used in the chain extension process is isophorone diamine.
In one embodiment of the invention, in the step (3), the mass ratio of the polyurethane emulsion, the acrylate monomer with flame retardant function, the initiator and the emulsifier is 50:10:1:1 to 50:3:0.3:0.2. the method comprises the steps of carrying out a first treatment on the surface of the
The initiator is one or more selected from ammonium persulfate, potassium persulfate, cumene hydroperoxide, tert-butyl hydroperoxide or benzoyl;
the emulsifier is selected from one or more of soaps, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyoxyethylene alkyl ether sulfate or polyoxyethylene alkyl ether.
In one embodiment of the present invention, in step (3), the reaction temperature during the polymerization reaction is 75 ℃; the reaction time was 3h.
In one embodiment of the invention, the polymerization process is under an inert atmosphere.
In one embodiment of the invention, the polymerization reaction is performed for 2 hours at a low temperature, the temperature is raised to 80 ℃, the temperature is kept for a period of time, and the temperature is reduced to 40-60 ℃ for discharging.
The present invention will be described in detail with reference to specific examples.
In the examples below, the reagents used were all commercially available unless otherwise specified; the detection means and method are conventional in the art.
Example 1
(1) Synthesis of acrylate monomer with flame retardant property
In a three neck round bottom flask at a ratio of 2: adding hydroxyethyl acrylate and diphenyl ethyl phosphate in proportion, adding 2% of p-toluenesulfonic acid catalyst and 0.1% of hydroquinone monomethyl ether polymerization inhibitor, heating by using an oil bath, reacting at 110 ℃ for 10 hours, and separating out a product by reduced pressure distillation after the reaction is finished.
(2) Synthesis of polyurethane emulsion with double bond
15g of polytetrahydrofuran ether polyol and 0.92g of dimethylolpropionic acid (DMPA) are decompressed and dehydrated for 2 hours at 120 ℃, cooled to 80 ℃, 7.6g of IPDI and 0.05% of dibutyltin dilaurate (DBTDL) are added under the protection of nitrogen, the reaction is carried out for about 3 hours, after NCO is titrated to a theoretical value by adopting a di-n-butylamine-toluene method, 0.75g of hydroxyethyl acrylate is added, and acetone is added according to the viscosity of the system in the reaction process; cooling to 40 ℃, adding 0.69g of TEA for neutralization, adding deionized water for emulsification under high-speed stirring, and adding 0.90g of isophorone diamine for chain extension to obtain polyurethane emulsion with double bonds, wherein the solid content of the polyurethane emulsion is about 30%.
(3) Synthesis of PUA composite emulsion
50g of the polyurethane emulsion obtained in the earlier stage and 0.7g of sodium dodecyl sulfonate serving as an emulsifier are added into a four-necked flask, the temperature is raised to about 75 ℃, 1g of the acrylate monomer (dissolved in 0.02g of ammonium persulfate) is added dropwise, the uniform dropwise addition is completed within 2 hours, the temperature is kept at 80 ℃ for reaction for 3 hours, and then the mixture is cooled and discharged.
Example 2
(1) Synthesis of acrylate monomer with flame retardant property
In a three neck round bottom flask at a ratio of 2:1 proportion of hydroxypropyl acrylate and triethyl phosphate, 2 percent of tetrabutyl titanate catalyst and 0.1 percent of hydroquinone monomethyl ether polymerization inhibitor are added, oil bath heating is adopted, the reaction temperature is 130 ℃, the reaction time is 8 hours, and the product is separated by reduced pressure distillation after the reaction is finished.
(2) Synthesis of polyurethane emulsion with double bond
30g of polycaprolactone polyol and 0.95g of DMPA are decompressed and dehydrated for 2 hours at 120 ℃, cooled to 40 ℃, added with 5.92g of TDI under the protection of nitrogen, reacted for 3 hours at 60 ℃, added with 0.84g of hydroxypropyl acrylate after NCO is titrated to a theoretical value by a di-n-butylamine-toluene method, and acetone is added according to the viscosity of the system in the reaction process; cooling to 40 ℃, adding 0.72g of TEA for neutralization, adding deionized water for emulsification under high-speed stirring, and adding 0.90g of isophorone diamine for chain extension to obtain polyurethane emulsion with double bonds, wherein the solid content of the polyurethane emulsion is about 30%.
(3) Synthesis of PUA composite emulsion
50g of the polyurethane emulsion obtained in the earlier stage and 0.5g of sodium dodecyl benzene sulfonate serving as an emulsifier are added into a four-necked flask, the temperature is raised to about 75 ℃, 3g of the acrylate monomer (dissolved in 0.06g of potassium persulfate) is dropwise added, the dropwise addition is completed within 2 hours, the temperature is kept at 80 ℃ for reaction for 3 hours, and then the mixture is cooled and discharged.
Example 3
(1) Synthesis of acrylate monomer with flame retardant property
In a three neck round bottom flask at a ratio of 2: adding hydroxyethyl methacrylate and tributyl phosphate in a proportion of 1, simultaneously adding 2% of an organotin catalyst and 0.1% of hydroquinone monomethyl ether polymerization inhibitor, heating by using an oil bath, reacting at 160 ℃ for 6 hours, and separating a product by reduced pressure distillation after the reaction is finished.
(3) Synthesis of polyurethane emulsion with double bond
12g of polytetrahydrofuran ether glycol, 5g of polycaprolactone glycol and 0.95g of DMPA are decompressed and dehydrated for 2 hours at 120 ℃, the temperature is reduced to 80 ℃, 4g of HDI, 2g of IPDI and 0.05% of DBTDL are added under the protection of nitrogen, the reaction is carried out for 3 hours, after the NCO is titrated to a theoretical value by adopting a di-n-butylamine-toluene method, 0.75g of hydroxyethyl acrylate is added, and acetone is added according to the viscosity of the system in the reaction process; cooling to 40 ℃, adding 0.72g of TEA for neutralization, adding deionized water for emulsification under high-speed stirring, and adding 0.90g of isophorone diamine for chain extension to obtain polyurethane emulsion with double bonds, wherein the solid content of the polyurethane emulsion is about 30%.
(3) Synthesis of PUA composite emulsion
50g of the polyurethane emulsion obtained in the earlier stage and 0.3g of sodium dodecyl sulfate serving as an emulsifier are added into a four-necked flask, the temperature is raised to about 75 ℃, 5g of the acrylic ester monomer (dissolved in 0.1g of ammonium persulfate) is dropwise added, the dropwise addition is completed within 2 hours, the temperature is kept at 80 ℃ for reaction for 3 hours, and then the mixture is cooled and discharged.
Comparative example 1
(1) Synthesis of acrylate monomers without flame retardant Properties
In a three neck round bottom flask at a ratio of 2: adding hydroxyethyl methacrylate and methyl methacrylate in a proportion of 1, simultaneously adding 2% of an organotin catalyst and 0.1% of hydroquinone monomethyl ether polymerization inhibitor, heating by using an oil bath, reacting at 160 ℃ for 6 hours, and separating a product by vacuum distillation after the reaction is finished.
(2) Synthesis of polyurethane emulsion with double bond
12g of polytetrahydrofuran ether polyol, 5.03g of polycaprolactone polyol and 0.92g of dimethylolpropionic acid (DMPA) are decompressed and dehydrated for 2 hours at 120 ℃, cooled to 80 ℃, 1.56g of Toluene Diisocyanate (TDI), 4.71g of IPDI and 0.05% of dibutyltin dilaurate (DBTDL) are added under the protection of nitrogen, the reaction is carried out for about 3 hours, after the NCO is titrated to a theoretical value by a di-n-butylamine-toluene method, 0.75g of hydroxyethyl acrylate is added, and acetone is added according to the viscosity of the system in the reaction process; cooling to 40 ℃, adding 0.69g of Triethylamine (TEA) for neutralization, adding deionized water for emulsification under high-speed stirring, and adding 0.90g of isophorone diamine for chain extension to obtain polyurethane emulsion with double bonds, wherein the solid content of the polyurethane emulsion is about 30%.
(3) Synthesis of PUA composite emulsion
50g of the polyurethane emulsion obtained in the earlier stage and 0.6g of sodium dodecyl sulfate serving as an emulsifier are added into a four-necked flask, the temperature is raised to about 75 ℃, 5g of the acrylic ester monomer (dissolved in 0.05g of ammonium persulfate) is dropwise added, the dropwise addition is completed within 2 hours, the temperature is kept at 80 ℃ for reaction for 3 hours, and then the mixture is cooled and discharged.
The performance tests of the products obtained in examples 1-4 are shown in the following table:
from the data in the table above, it can be seen that the higher the content of the flame-retardant functional monomer in the composite emulsion, the higher the limiting oxygen index thereof, i.e. the better the flame-retardant property.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (8)
1. The intrinsic flame-retardant polyurethane-acrylate emulsion is characterized by being prepared by polymerization reaction of an acrylate monomer with a flame-retardant function and a polyurethane emulsion containing double bonds;
the acrylate monomer with the flame-retardant function comprises the following raw material components in percentage by mass: 20-85% of monohydroxy acrylate monomer, 1-15% of flame-retardant functional monomer, 0.5-3% of catalyst and the balance of polymerization inhibitor;
the polyurethane emulsion comprises the following raw materials in percentage by mass: 10-40% of diisocyanate, 20-80% of oligomer polyol, 0.01-0.3% of dibutyltin dilaurate, 2.8-4.5% of dimethylolpropionic acid and 2.5-10% of chain extender, and further comprises a monohydroxyacrylate monomer, wherein the molar ratio of diisocyanate, oligomer polyol, dimethylolpropionic acid and monohydroxyacrylate monomer is 9:3:1.5: 0.8-6: 3:1.5:0.9;
the preparation method of the intrinsic flame-retardant polyurethane-acrylate emulsion comprises the following steps:
(1) Preparation of acrylate monomer with flame retardant property: uniformly mixing a monohydroxy acrylic ester monomer and a flame-retardant functional monomer, and then adding a catalyst and a polymerization inhibitor; after the transesterification reaction, an acrylic ester monomer with flame retardant property is obtained;
(2) Preparation of polyurethane emulsion: uniformly mixing diisocyanate, oligomer polyol and dimethylolpropionic acid, then adding dibutyltin dilaurate and a monohydroxy acrylic ester monomer, performing a prepolymerization reaction to obtain a prepolymer containing double bonds, and performing post-treatment to obtain polyurethane emulsion;
(3) Preparation of an intrinsic flame retardant polyurethane-acrylate emulsion: and (3) taking the polyurethane emulsion prepared in the step (2) as seeds, and carrying out polymerization reaction with the acrylate monomer with the flame retardant function, the initiator and the emulsifier prepared in the step (1) to obtain the intrinsic flame retardant polyurethane-acrylate emulsion.
2. An intrinsically flame retardant polyurethane-acrylate emulsion according to claim 1 wherein in step (1) the monohydroxyacrylate monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate or hydroxypropyl acrylate;
the flame-retardant functional monomer is selected from one or more of diphenyl ethyl phosphate, triethyl phosphate, tributyl phosphate, toluene diphenyl phosphate, trimethylol phosphorus oxide, dibromo neopentyl glycol or DOPO-hydroquinone;
the catalyst is one or more selected from sodium methoxide, p-toluenesulfonic acid, organic tin, zinc isooctanoate, tetraethyl titanate or tetrabutyl titanate;
the polymerization inhibitor is selected from one or more of hydroquinone monomethyl ether, hydroquinone, phenothiazine or nitroxide free radical polymerization inhibitors.
3. An intrinsically flame retardant polyurethane-acrylate emulsion according to claim 1 wherein in step (1) the molar ratio of monohydroxyacrylate monomer to flame retardant functional monomer is 1.5: 1-1: 2.
4. the intrinsic flame retardant polyurethane-acrylate emulsion of claim 1, wherein in step (1), the reaction temperature is 110-160 ℃ during the transesterification reaction; the reaction time is 6-10h.
5. An intrinsically flame retardant polyurethane-acrylate emulsion according to claim 1 wherein in step (2) the diisocyanate is selected from one or more of hexamethylene diisocyanate, isophorone diisocyanate, toluene diisocyanate, diphenylmethane-4, 4-diisocyanate, 4-dicyclohexylmethane diisocyanate or terephthal-diisocyanate;
the low polymer polyol is selected from one or more of polytetrahydrofuran ether glycol, polycaprolactone glycol, polyethylene glycol, polypropylene glycol, polycarbonate glycol, polyethylene glycol adipate glycol or polybutylene adipate;
the monohydroxy acrylic ester monomer is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, glycidyl methacrylate or N-methylolacrylamide.
6. The intrinsic flame retardant polyurethane-acrylate emulsion according to claim 1, wherein in step (2), the reaction temperature is 70-90 ℃ in the prepolymerization reaction process; the reaction time is 4-6 hours.
7. The intrinsically flame retardant polyurethane-acrylate emulsion of claim 1, wherein in step (3), the mass ratio of polyurethane emulsion, acrylate monomer with flame retardant function, initiator and emulsifier is 50:10:1: 1-50: 3:0.3:0.2;
the initiator is one or more selected from ammonium persulfate, potassium persulfate, cumene hydroperoxide, tert-butyl hydroperoxide or benzoyl;
the emulsifier is selected from one or more of soaps, sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, polyoxyethylene alkyl ether sulfate or polyoxyethylene alkyl ether.
8. The intrinsic flame retardant polyurethane-acrylate emulsion of claim 1, wherein in step (3), the reaction temperature is 70-80 ℃ during the polymerization reaction; the reaction time is 2.5-3.5 h.
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| CN107286306A (en) * | 2017-07-25 | 2017-10-24 | 东莞长联新材料科技股份有限公司 | A kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof |
| CN113122121A (en) * | 2021-04-23 | 2021-07-16 | 中科院广州化学有限公司 | Phosphorus-containing polyurethane-acrylic resin flame-retardant coating with semi-interpenetrating network structure and preparation method and application thereof |
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| CN103360561A (en) * | 2013-07-02 | 2013-10-23 | 广东海顺新材料科技有限公司 | Polyurethane modified acrylic emulsion, preparation method of acrylic emulsion and prepared artificial stone |
| CN107286306A (en) * | 2017-07-25 | 2017-10-24 | 东莞长联新材料科技股份有限公司 | A kind of aqueous polyurethane acrylate copolymer emulsion and preparation method thereof |
| CN113122121A (en) * | 2021-04-23 | 2021-07-16 | 中科院广州化学有限公司 | Phosphorus-containing polyurethane-acrylic resin flame-retardant coating with semi-interpenetrating network structure and preparation method and application thereof |
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