CN112480856A - Phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive and preparation method and application thereof - Google Patents
Phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive and preparation method and application thereof Download PDFInfo
- Publication number
- CN112480856A CN112480856A CN202011374256.0A CN202011374256A CN112480856A CN 112480856 A CN112480856 A CN 112480856A CN 202011374256 A CN202011374256 A CN 202011374256A CN 112480856 A CN112480856 A CN 112480856A
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- China
- Prior art keywords
- water
- retardant adhesive
- flame
- flame retardant
- copolymer
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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 60
- 239000003063 flame retardant Substances 0.000 title claims abstract description 57
- 239000000853 adhesive Substances 0.000 title claims abstract description 56
- 230000001070 adhesive effect Effects 0.000 title claims abstract description 56
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 38
- 239000004814 polyurethane Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GDFCWFBWQUEQIJ-UHFFFAOYSA-N [B].[P] Chemical compound [B].[P] GDFCWFBWQUEQIJ-UHFFFAOYSA-N 0.000 title description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229920001577 copolymer Polymers 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 23
- 229920002472 Starch Polymers 0.000 claims abstract description 19
- 239000008107 starch Substances 0.000 claims abstract description 19
- 235000019698 starch Nutrition 0.000 claims abstract description 19
- 239000000945 filler Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims description 22
- 239000000123 paper Substances 0.000 claims description 20
- 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 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- 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
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 8
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 230000003472 neutralizing effect Effects 0.000 claims description 5
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000001254 oxidized starch Substances 0.000 claims description 3
- 235000013808 oxidized starch Nutrition 0.000 claims description 3
- 239000008096 xylene Substances 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims 3
- 239000013530 defoamer Substances 0.000 claims 2
- DEFTVJAJYJMJNL-UHFFFAOYSA-N P(=O)(=O)B Chemical group P(=O)(=O)B DEFTVJAJYJMJNL-UHFFFAOYSA-N 0.000 claims 1
- 238000006386 neutralization reaction Methods 0.000 claims 1
- 239000000454 talc Substances 0.000 claims 1
- 229910052623 talc Inorganic materials 0.000 claims 1
- 239000000779 smoke Substances 0.000 abstract description 5
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract 1
- 230000005923 long-lasting effect Effects 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000004321 preservation Methods 0.000 description 9
- 229910052796 boron Inorganic materials 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 8
- 229910052698 phosphorus Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 238000002485 combustion reaction Methods 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000013461 design Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002518 antifoaming agent Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- YFPJFKYCVYXDJK-UHFFFAOYSA-N Diphenylphosphine oxide Chemical compound C=1C=CC=CC=1[P+](=O)C1=CC=CC=C1 YFPJFKYCVYXDJK-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- JLGNDWRTUGPNRE-UHFFFAOYSA-N [B]=O.[P] Chemical compound [B]=O.[P] JLGNDWRTUGPNRE-UHFFFAOYSA-N 0.000 description 1
- JQYOCVPEXWBLGO-UHFFFAOYSA-N [N].[Si].[P] Chemical compound [N].[Si].[P] JQYOCVPEXWBLGO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000011111 cardboard Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- -1 nitrogen containing compound Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000011087 paperboard Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—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
- 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
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having 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
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/04—Non-macromolecular additives inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
本发明公开了磷硼杂链羟端基预聚物嵌段聚氨酯阻燃粘合剂及其制备方法与应用，粘合剂各组分的质量百分如下：85.0～95.0％水性基料，4.0～12.0％填料，1.0～3.0％助剂，水性基料由磷硼杂链预聚物嵌段聚氨酯水性共聚物及水溶性淀粉组成，所述水溶性淀粉的质量占水性基料质量的40.0～45.0％。本发明示例的粘合剂，通过分子设计与合成，以制备低毒环保、低烟无卤、长效阻燃和粘接增强的瓦楞纸箱阻燃粘合剂。The invention discloses a phosbora chain hydroxyl end group prepolymer block polyurethane flame retardant adhesive and a preparation method and application thereof. The mass percentage of each component of the adhesive is as follows: 85.0-95.0% of water-based ～12.0% filler, 1.0～3.0% auxiliary, the water-based base material is composed of phosphobora chain prepolymer block polyurethane water-based copolymer and water-soluble starch, and the quality of the water-soluble starch accounts for 40.0～40% of the quality of the water-based base material. 45.0%. The adhesive exemplified in the present invention is designed and synthesized to prepare a low-toxicity, environment-friendly, low-smoke, halogen-free, long-lasting flame-retardant and adhesive-enhanced flame-retardant adhesive for corrugated boxes.
Description
Technical Field
The invention relates to a phosphorus-boron heterochain prepolymer block polyurethane flame-retardant adhesive as well as a preparation method and application thereof, belonging to the technical field of adhesive preparation.
Background
The paper material is natural organic polymer material, and its main component is plant fiber (general formula is (C)6H10O5)n). The fire point of the paper is about 130 ℃, the Limiting Oxygen Index (LOI) is only about 15, the paper belongs to inflammables, the paper is inflammable when meeting fire, and fire hazard exists in the using process, so that the fire retardation and fire prevention of the paper are always influenced by scientific and technological industries at home and abroadThe author and the engineer pay high attention to it. The corrugated paper packing box is an important direction for paper application, according to the structural form and the manufacturing process of the corrugated paper box, a large amount of adhesives are used for adhering corrugated medium paper and surface paper in the manufacturing process of the corrugated paper box, the corrugated medium paper and the surface paper adhered by the adhesives form a corrugated paper board manufactured by the corrugated paper box, and in the manufacturing process of the corrugated paper box, the flame retardance of the corrugated packing box can be realized by adopting the flame-retardant adhesives, the flame-retardant level of the corrugated packing box is improved, and the fire risk of the corrugated paper box and packed articles is reduced.
Researches show that elements such as halogen (X), phosphorus (P), boron (B), nitrogen (N), silicon (Si) and the like have excellent flame retardant effect in the combustion process of organic materials, but the flame retardant containing the elements such as P, B, N, Si has the flame retardant function of halogen-free low-smoke, environmental protection and high efficiency because the flame retardant containing the elements X is limited due to the generation of high-toxicity gas in the combustion process, and the elements such as P, B, N, Si and the like are subjected to molecular design and synthesis to synthesize the polymer with the intrinsic flame retardant function, so that the preparation method is an effective way for preparing the halogen-free low-smoke long-acting flame retardant high polymer material. P, B, N, Si, and the like, have different flame retardant mechanisms and mechanisms, and in the combustion process, phosphorus element exerts flame retardant effect through a condensed phase blocking and isolating mechanism for promoting carbonization to form coke and a gas phase inactivation passivation mechanism for quenching free radicals; boron and silicon elements generate high-stability glass layers (boronized glass and silicified glass) in the combustion process, and the flame-retardant effect is exerted through a glass layer condensation phase isolation blocking mechanism; nitrogen element plays a flame-retardant function mainly through a gas-phase dilution mechanism for reducing the oxygen concentration in a combustion zone in the combustion process. In technical application, through molecular design and synthesis, two or more elements with different flame-retardant mechanisms are combined, and the synergistic effect of multiple flame-retardant mechanisms can be achieved.
For this reason, many developers have conducted studies on the preparation of adhesives based on the combination of elements such as P, B, N, Si. For example, chinese patent document "201810561651.6" discloses a novel flame retardant binder of plant fiber and a preparation method thereof, and specifically discloses that the novel flame retardant binder of plant fiber comprises the following components in parts by weight: 1-4 parts of trisodium phosphate, 30-75 parts of magnesium sulfate solution, 1-5 parts of calcium hydroxide, 1-4 parts of emulsifier, 20-80 parts of starch glue, 10-30 parts of phenolic resin, 2-4 parts of tartaric acid, 1-3 parts of boric acid, 118 parts of magnesium oxide, 2-5 parts of silicon dioxide and 1-3 parts of colorant; the concentration of the magnesium sulfate solution is 17-25 DEG Be of baume degree, and the preparation method of the starch glue comprises the following steps: mixing starch and water according to a mass ratio of 0.12-0.2: 1, heating and pasting according to the proportion of 1; chinese patent document '201210479147.4' discloses a phosphorus-silicon-nitrogen ternary synergistic flame retardant, a preparation method and application thereof, wherein an organic boron catalyst is used, diphenyl phosphine oxide and derivatives thereof and silazane containing carbon-carbon double bonds are subjected to addition reaction to prepare a novel phosphorus, silicon and nitrogen containing compound and the like.
The invention is researched on the basis of the prior art and aims to obtain the corrugated case board paper adhesive with the flame-retardant effect.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a phosphorus-boron hybrid chain prepolymer block polyurethane copolymer corrugated case flame-retardant adhesive and a preparation method thereof, and the corrugated case flame-retardant adhesive with low toxicity, environmental protection, low smoke, no halogen, long-acting flame retardance and bonding enhancement is prepared by molecular design and synthesis.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive is characterized by comprising the following components in percentage by mass: 85.0-95.0% of water-based base material; 4.0-12.0% of filler; 1.0-3.0% of an auxiliary agent; the water-based base material consists of a phosphorus-boron heterochain prepolymer segmented polyurethane water-based copolymer and water-soluble starch, wherein the mass of the water-soluble starch accounts for 40.0-45.0% of that of the water-based base material;
the preparation method of the copolymer comprises the following steps:
(1) adding a phosphorus-boron hybrid chain prepolymer (PDCP-DGB) into a solvent, adding a catalyst, mixing and stirring, heating and preserving heat under a protective atmosphere, wherein the heating temperature is 63-67 ℃, the heating mode is water bath heating, and the preserving heat time is 30-35 min;
(2) dropwise adding Toluene Diisocyanate (TDI) and dimethylolpropionic acid (DMPA) into the solution obtained in the step (1) in the heat preservation process in the step (1), preserving heat after heating, and separating a solvent, wherein the temperature of the system after heating is 73-77 ℃, and the heat preservation time is 1.5-2.5 h;
(3) and (3) cooling the solution obtained in the step (2), keeping the temperature, adding a neutralizing agent and water into the solution to adjust the pH, and continuously stirring to obtain the solution, wherein the temperature of the cooled system is 43-47 ℃, the pH value of the neutralized solution is 7.5-9.0, and the stirring time is 1-1.5 h.
Further, the water-soluble starch is oxidized starch or etherified starch.
Further, the filler is one or more of calcium carbonate, barium sulfate and talcum powder.
Further, the auxiliary agent is a defoaming agent, and preferably, the defoaming agent is polymethyl silicone oil or tributyl phosphate.
Further, the number average molecular weight of the phosphorus boron heterochain prepolymer
The distribution index is 1.1-1.2.
Further, the copolymer comprises the following components in percentage by mass: 75.9-76.9% of phosphorus-boron hybrid chain prepolymer; 16.2-17.3% of toluene diisocyanate; 6.8-6.9% of dimethylolpropionic acid.
Further, the solvent is xylene.
Furthermore, the catalyst is dibutyltin dilaurate, and the mass ratio of dibutyltin dilaurate to toluene diisocyanate is 1.0: 0.01-0.03.
Further, the neutralizing agent is one of monoethanolamine, diethanolamine, monoethylamine and diethylamine.
Further, the copolymer has a structural formula:
a method of preparing a flame retardant adhesive comprising: uniformly mixing the copolymer and the water-soluble starch in a heat preservation state, and cooling to prepare a water-based base material; and (3) mixing and stirring the water-based base material, the filler and the auxiliary agent uniformly, and adjusting the viscosity of the mixture to obtain the flame-retardant adhesive.
Further, the viscosity of the adjusted adhesive is 2500-3000 Cp at a temperature of 25 ℃.
The application of the flame-retardant adhesive in the preparation of corrugated cases.
The principle of the prepared corrugated case flame-retardant adhesive is as follows:
taking phosphorus-boron heterochain prepolymer, toluene diisocyanate and dimethylolpropionic acid as raw materials, and gradually polymerizing under the catalysis of dibutyltin dilaurate to obtain phosphorus-boron heterochain prepolymer segmented polyurethane copolymer; then neutralizing a neutralizer and the phosphorus-boron hybrid chain prepolymer segmented polyurethane copolymer to form salt, and compounding the salt with water-soluble starch, a filler and an auxiliary agent to prepare the phosphorus-boron hybrid chain prepolymer segmented polyurethane copolymer flame-retardant adhesive.
Compared with the prior art, the invention has the beneficial effects that:
1. through molecular design and synthesis, phosphorus-boron flame-retardant elements and hydrophilic groups are bonded in a polyurethane molecular structure in a chemical bond form to prepare a phosphorus-boron heterochain block polyurethane aqueous copolymer, and the flame-retardant performance and the waterproof property of the polymer are effective for a long time as the polymer molecular chain is not degraded into micromolecules in the polymer molecular chain; meanwhile, no halogen element is contained in a molecular chain, phosphate, borate and even phosphorus boron oxide are generated through oxidation in the high-temperature decomposition process, the adhesive prepared by taking the water-based copolymer as a base material has the characteristics of low toxicity, environmental protection, low smoke, no halogen, long-acting flame retardance and enhanced adhesion, and is used for corrugated case board paper adhesion to endow corrugated case packaging products with synergistic functions of long-acting flame retardance and enhanced adhesion.
2. By adding the filler, the size stability of the adhesive after curing is improved, and the production cost of the adhesive is reduced.
Detailed Description
It is to be understood that the specific embodiments described herein are merely illustrative of the relevant invention and not restrictive of the invention.
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict.
A boron heterochain prepolymer block polyurethane water-based copolymer has a structural formula as follows:
the copolymer is obtained by reacting and polymerizing phosphorus-boron heterochain prepolymer, toluene diisocyanate and dimethylolpropionic acid according to a certain mass ratio, and the synthetic route of the copolymer is as follows:
the copolymer can be used for preparing a flame-retardant adhesive, and the adhesive is prepared by compounding the copolymer, water-soluble starch, filler and an auxiliary agent according to a certain mass ratio.
The first embodiment is as follows:
in this embodiment, the preparation method of the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive comprises the following steps:
firstly, preparing a phosphorus-boron heterochain prepolymer block polyurethane aqueous copolymer:
(1) adding 100ml of dimethylbenzene serving as a solvent, 151.8g of PDCP-DGB and dibutyltin dilaurate with the TDI substance in a quantitative ratio of 1:0.01 into a four-neck flask with a mechanical stirring device, a nitrogen protection device, a condensation reflux device, a water bath heating device and a temperature control device, stirring, introducing nitrogen, heating to 65 +/-1 ℃ in a water bath, and keeping the temperature for 33 min;
(2) dropwise adding 34.6g of TDI and 13.6g of DMPA into the solution obtained in the step (1) in the heat preservation process in the step (1), wherein the TDI and the DMPA are required to be dropwise added in 30min, the temperature of the system is kept at 73 +/-1 ℃ after the TDI and the DMPA are added, the heat preservation time is 2.5h, and the dimethylbenzene is separated and recovered;
(3) cooling the solution obtained in the step (2) to 45 +/-1 ℃, adding monoethanolamine and 50ml of water, adjusting the pH value of the solution to 9.0, and continuously stirring for 1h to obtain a phosphorus-boron hybrid chain prepolymer segmented polyurethane copolymer;
secondly, preparing a phosphorus-boron hybrid chain prepolymer block polyurethane copolymer aqueous base material:
(4) taking 125g of the copolymer obtained in the step (3), adding 100g of oxidized starch into the copolymer, keeping the temperature at 45 +/-1 ℃, continuing stirring for 0.5min, stopping stirring, cooling and discharging to obtain a phosphorus-boron hybrid chain prepolymer block polyurethane copolymer aqueous base material;
and thirdly, preparing the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive:
(5) and (3) weighing 85.0g of the aqueous base material prepared in the step (4), 12.0g of calcium carbonate and 3.0g of tributyl phosphate, mixing in a container, strongly stirring and uniformly dispersing, and adjusting the viscosity of the adhesive to be 2510Cp (25 ℃) by using water to obtain the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive.
Example two:
in this embodiment, the preparation method of the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive comprises the following steps:
firstly, preparing a phosphorus-boron heterochain prepolymer block polyurethane aqueous copolymer:
(1) adding 100ml of dimethylbenzene serving as a solvent, 153.8g of PDCP-DGB and dibutyltin dilaurate with the TDI substance in a mass ratio of 1:0.03 into a four-neck flask with a mechanical stirring device, a nitrogen protection device, a condensation reflux device, a water bath heating device and a temperature control device, stirring, introducing nitrogen, heating to 63 +/-1 ℃ in a water bath, and keeping the temperature for 35 min;
(2) dropwise adding 32.4g of TDI and 13.8g of DMPA into the solution obtained in the step (1) in the heat preservation process in the step (1), wherein the TDI and the DMPA are required to be dropwise added in 30min, the temperature of the system is kept at 77 +/-1 ℃ after the addition, the heat preservation time is 1.5h, and the xylene is separated and recovered;
(3) cooling the solution obtained in the step (2) to 43 +/-1 ℃, adding monoethanolamine and 50ml of water, adjusting the pH value of the solution to 7, and continuing stirring for 1.3h to obtain a phosphorus-boron hybrid chain prepolymer segmented polyurethane copolymer;
secondly, preparing a phosphorus-boron hybrid chain prepolymer block polyurethane copolymer aqueous base material:
(4) taking 130g of the copolymer obtained in the step (3), adding 100g of etherified starch into the copolymer, keeping the temperature at 43 +/-1 ℃, continuing stirring for 0.5min, stopping stirring, cooling and discharging to obtain a phosphorus-boron hybrid chain prepolymer block polyurethane copolymer aqueous base material;
and thirdly, preparing the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive:
(5) and (3) weighing 90.0g of the water-based base material prepared in the step (4), 8.0g of talcum powder and 2.0g of tributyl phosphate, mixing in a container, strongly stirring and uniformly dispersing, and adjusting the viscosity of the adhesive to be 2980Cp (25 ℃) by using water to obtain the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive.
Example three:
in this embodiment, the preparation method of the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive comprises the following steps:
firstly, preparing a phosphorus-boron heterochain prepolymer block polyurethane aqueous copolymer:
(1) adding 100ml of dimethylbenzene serving as a solvent, 152.0g of PDCP-DGB and dibutyltin dilaurate with the TDI substance in a mass ratio of 1:0.02 into a four-neck flask with a mechanical stirring device, a nitrogen protection device, a condensation reflux device, a water bath heating device and a temperature control device, stirring, introducing nitrogen, heating to 67 +/-1 ℃ in a water bath, and keeping the temperature for 30 min;
(2) dropwise adding 34.0g of TDI and 13.6g of DMPA into the solution obtained in the step (1) in the heat preservation process in the step (1), wherein the TDI and the DMPA are required to be dropwise added in 30min, the temperature of the system is kept at 75 +/-1 ℃ after the TDI and the DMPA are added, the heat preservation time is 2h, and the dimethylbenzene is separated and recovered;
(3) cooling the solution obtained in the step (2) to 47 +/-1 ℃, adding monoethanolamine and 50ml of water, adjusting the pH value of the solution to 8, and continuously stirring for 1.5h to obtain a phosphorus-boron hybrid chain prepolymer segmented polyurethane copolymer;
secondly, preparing a phosphorus-boron hybrid chain prepolymer block polyurethane copolymer aqueous base material:
(4) taking 150g of the copolymer obtained in the step (3), adding 100g of etherified starch into the copolymer, keeping the temperature at 47 +/-1 ℃, continuing stirring for 0.5min, stopping stirring, cooling and discharging to obtain a phosphorus-boron hybrid chain prepolymer block polyurethane copolymer aqueous base material;
and thirdly, preparing the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive:
(5) and (3) weighing 95.0g of the aqueous base material prepared in the step (4), 4.0g of barium sulfate and 1.0g of polymethylsilicone oil, mixing in a container, strongly stirring and uniformly dispersing, and adjusting the viscosity of the adhesive to 2750Cp (25 ℃) by using water to obtain the phosphorus-boron hybrid chain prepolymer block polyurethane flame-retardant adhesive.
And (3) performance testing:
cone calorimeter and Limiting Oxygen Index (LOI) measurements were made on corrugated board bonded with the phosphorus boron heterochain prepolymer segmented polyurethane flame retardant adhesive according to ISO5660-1 and ASTM D2863-97, and the results of the various performance indices are shown in Table 1.
TABLE 1
As can be seen from Table 1, the flame retardant performance of the five-layer corrugated cardboard board prepared by the adhesive bonding agent in the embodiment reaches the flame retardant level specified in GB/T14656-2009 standard, and the water absorption of the sizing paper is obviously reduced.
The above description is only a preferred embodiment of the application and is illustrative of the principles of the technology employed. It will be appreciated by a person skilled in the art that the scope of the invention as referred to in the present application is not limited to the embodiments with a specific combination of the above-mentioned features, but also covers other embodiments with any combination of the above-mentioned features or their equivalents without departing from the inventive concept. For example, the above features may be replaced with (but not limited to) features having similar functions disclosed in the present application.
Other technical features than those described in the specification are known to those skilled in the art, and are not described herein in detail in order to highlight the innovative features of the present invention.
Claims (10)
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