CN105504196A - Flame-retardant polyurethane resin for synthetic leather and preparation method of flame-retardant polyurethane resin - Google Patents

Flame-retardant polyurethane resin for synthetic leather and preparation method of flame-retardant polyurethane resin Download PDF

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Publication number
CN105504196A
CN105504196A CN201510981218.4A CN201510981218A CN105504196A CN 105504196 A CN105504196 A CN 105504196A CN 201510981218 A CN201510981218 A CN 201510981218A CN 105504196 A CN105504196 A CN 105504196A
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glycol
polyurethane resin
synthetic leather
polyol
retardant polyurethane
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Inventor
谢品成
杨银龙
蒋红梅
唐劲松
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Shanghai Huafon New Material Research & Development Technology Co., Ltd.
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Shanghai Huafeng Material Science And Technology Research Institute (limited Partnership)
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4854Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203Polyhydroxy compounds
    • C08G18/3206Polyhydroxy compounds aliphatic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/38Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3802Low-molecular-weight compounds having heteroatoms other than oxygen having halogens
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/38Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/4009Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4018Mixtures of compounds of group C08G18/42 with compounds of group C08G18/48
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/42Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633Compounds of group C08G18/42
    • C08G18/6637Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203

Abstract

The invention discloses flame-retardant polyurethane resin for synthetic leather and a preparation method of the flame-retardant polyurethane resin. The flame-retardant polyurethane resin for the synthetic leather is prepared from components in percentage by mass as follows: 8%-30% of polyvalent alcohol, 2%-10% of flame-retardant polyol, 0.5%-5% of small molecular polyol, 6%-12% of diisocyanate, 55%-80% of an organic solvent, 0.05%-0.15% of a terminating agent, 0.05%-0.1% of a catalyst and 0.05%-0.1% of an auxiliary, wherein the polyvalent alcohol is selected from more than one of polyether polyol or polyester polyol, the number-average molar mass of the polyether polyol is 400-2,000, and the number-average molar mass of the polyester polyol is 500-3,000; the flame-retardant polyol is selected from one or more of phosphorus-containing polyol and halogen-containing polyol with the functionality degree of 2 and the number-average molar mass of 100-1,000. The flame retardant property of the polyurethane resin applied to ultra-fiber synthetic leather is effectively improved; the prepared flame-retardant superfine fiber synthetic leather can be widely applied to the fields of home decoration, automotive trim and the like.

Description

Use for synthetic leather flame retardant polyurethane resin and preparation method thereof
Technical field
The present invention relates to a kind of use for synthetic leather flame retardant polyurethane resin and preparation method thereof.
Background technology
Along with urethane resin popularizing in synthetic leather Application Areas, some new fields such as demand to Synthetic Leather such as home decoration, automotive trim increases sharply, because the flame retardant properties of polyurethane material own is not good, in order to the fire losses making Synthetic Leather cause in the field such as home decoration, automotive trim is minimum, normally fire-retardant finish is carried out to meet the high flame resistance requirement of such high-end field to synthetic leather material to household or interior material.
Patent CN201310689458 and CN201510510077 all adopts and add additional fire retardant in use for synthetic leather resin, although this kind of method improves the fire-retardant index of synthetic leather material to a certain extent, but because the consistency of fire-retardant filler and urethane is poor, and a large amount of interpolation fire-retardant filler (general addition more than 30%) very easily causes fire-retardant filler at skewness in urethane, the consequence such as cause that fire-retardant filler is separated out in synthetic leather, seriously undermines mechanical property and the apparent property of Synthetic Leather.
Summary of the invention
The object of this invention is to provide a kind of use for synthetic leather flame retardant polyurethane resin and preparation method thereof, to overcome the deficiencies in the prior art.
Described flame retardant polyurethane resin adopts the component of following mass percent to prepare:
The per-cent sum of each component is 100%.
Described polyvalent alcohol is more than one in polyether glycol or polyester polyol.
Described polyether glycol is selected from the PTMG that number-average molecular weight is 400 ~ 2000, and preferred number average molecular weight is the PTMG of 2000.
It is 500 ~ 3000 that described polyester polyol is selected from number-average molecular weight, preferred number average molecular weight is the poly-hexanodioic acid-1 of 2000, 4 butanediol ester glycol, polyethylene glycol adipate glycol, polypropylene adipate (PPA) glycol, poly-hexanodioic acid-1, 6 hexylene glycol esterdiols, polyneopentyl glycol adipate glycol, poly-adipate glycol butanediol ester glycol, poly-adipate glycol propylene glycol ester glycol, poly-hexanodioic acid hexylene glycol neopentyl glycol esterdiol, polybutyleneadipate hexylene glycol esterdiol, polybutyleneadipate neopentyl glycol esterdiol, one or more mixing in poly-own Inner esterdiol, blending ratio is not limit.
Described flame-proof polyol be phosphorus-containing polyol, Halogen polyvalent alcohol one or more, preferred functionality is 2, number-average molecular weight be the phosphorus-containing polyol of 100-1000, Halogen polyvalent alcohol one or more, more preferably commodity are called one or more mixing in ExolitOP550, ExolitOP560, PHT4Diol, SaytexRB-79, Firemaster520, IXOLM125 or IXOLB251, and blending ratio is not limit.
Described small molecule polyol is C 2-6aliphatic diol one or more, blending ratio is not limit.
Described vulcabond is 4,4-'-diphenylmethane diisocyanate MDI, tolylene diisocyanate TDI, tolylene diisocyanate XDI, 1,5-is vulcabond NDI, PPDI PPDI, hexamethylene diisocyanate HDI, hydrogenation 4,4-'-diphenylmethane diisocyanate H how 12one or more in MDI.
Described organic solvent is one or more mixing in DMF, N,N-dimethylacetamide, toluene, butanone, vinyl acetic monomer, N-BUTYL ACETATE, and blending ratio is not limit.
Described terminator is single functionality alcohols, particular methanol.
Described catalyzer is dibutyl tin dilaurate, stannous octoate or BiCAT8118.
Described auxiliary agent is one or more in oxidation inhibitor, flow agent, slipping agent, UV light absorber.
The preparation method of described use for synthetic leather flame retardant polyurethane resin, comprises the steps:
(1) by more than one in polyether glycol or polyester polyol, flame-proof polyol, small molecule polyol, part organic solvent and auxiliary agent 45 ~ 55 DEG C of mixing, add vulcabond again, react at 70 ~ 80 DEG C, the reaction times is 2h ~ 4 hour;
Described part organic solvent is 30% ~ 50% of organic solvent total mass;
(2) and then add vulcabond, catalyzer and residual solvent, at 70 ~ 80 DEG C reaction until soltion viscosity is 30000 ~ 60000mPas; Add terminator end-blocking, stir, namely obtain described use for synthetic leather flame retardant polyurethane resin;
Contriver finds, for the polyether glycol that the present invention relates to and polyester polyol, and the flame-proof polyol of not all can produce good flame retardant effect, test proves, only in the ammonia ester molecule chain backbone prepared for starting raw material with described polyether glycol and polyester polyol, introduce the polyol with described flame retardant properties, the flame retardant properties of urethane resin in the application of superfluorescent fiber synthetic leather can be improved.
Instant invention overcomes traditional method and add fire-retardant filler to the disadvantageous effect of polyurethane integral performance, effectively raise the flame retardant properties of urethane resin in the application of superfluorescent fiber synthetic leather.Fire-retardant superfine fiber chemical leather prepared by the present invention can be widely used in the field such as home decoration, automotive trim.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be appreciated that, these embodiments only for illustrating the present invention, and are not intended to limit the scope of the invention.The improvement made according to the present invention of technician and adjustment, still belong to protection scope of the present invention in actual applications.Following examples are raw materials used be commercially available.
In embodiment, flame retardant rating carries out flame retardant properties detection according to GB8410 standard to sample.
Embodiment 1
Raw materials used and the quality of the present embodiment is in table 1.
Table 1
Preparation method:
By BHT, PTMG, ExolitOP550,1, the N of 4-butyleneglycol, total mass 36.5%, dinethylformamide drops in reactor together, 45 DEG C stir, add 4 again, 4-'-diphenylmethane diisocyanate, insulation reaction at 70 DEG C, add MDI after 2h, drip dibutyl tin dilaurate catalyzer, add remaining N simultaneously, dinethylformamide and butanone, at 80 DEG C, reaction is until soltion viscosity is 30000mPas, adds methyl alcohol end-blocking, namely obtains described use for synthetic leather flame retardant polyurethane resin after stirring.
Embodiment 2
Raw materials used and the quality of the present embodiment is in table 2.
Table 2
The preparation process of the use for synthetic leather flame retardant polyurethane resin of the present embodiment is as follows:
By antioxidant 1010, polyethylene glycol adipate glycol, ExolitOP560,1, the N of 4-butyleneglycol, 36.5% quality, dinethylformamide drops in reactor together, 55 DEG C stir, add 4 again, 4-'-diphenylmethane diisocyanate, insulation reaction at 80 DEG C, add MDI after 2h, drip stannous octoate catalyst, add residue N simultaneously, dinethylformamide and ethyl acetate, at 70 DEG C, reaction is until soltion viscosity is 40000mPas, adds methyl alcohol end-blocking, namely obtains described use for synthetic leather flame retardant polyurethane resin after stirring.
Embodiment 3
Raw materials used and the quality of the present embodiment is in table 3.
Table 3
The preparation process of the use for synthetic leather flame retardant polyurethane resin of the present embodiment is as follows:
By BHT, PTMG (number-average molecular weight 2000), polypropylene adipate (PPA) glycol (number-average molecular weight 2000), SaytexRB-79, 1, 4-butyleneglycol, the N of 36.5% quality, dinethylformamide drops in reactor together, 50 DEG C stir, add 4 again, 4-'-diphenylmethane diisocyanate, insulation reaction at 75 DEG C, 4 are added after 2h, 4-'-diphenylmethane diisocyanate, drip CAT8118, add remaining N again, dinethylformamide and butanone, reaction is until soltion viscosity is 45000mPas, add methyl alcohol end-blocking, stir, after namely obtain described use for synthetic leather flame retardant polyurethane resin.
Embodiment 4
Raw materials used and the quality of the present embodiment is in table 4.
Table 4
The preparation process of the use for synthetic leather flame retardant polyurethane resin of the present embodiment is as follows:
By BHT, PTMG (number-average molecular weight 2000), poly-hexanodioic acid-1, 6-hexylene glycol esterdiol (number-average molecular weight 2000), PHT4Diol, 1, 4-butyleneglycol, the N of 36.5% quality, dinethylformamide drops in reactor together, 55 DEG C stir, add 4 again, 4-'-diphenylmethane diisocyanate, insulation reaction at 80 DEG C, after 2h, add 4 of surplus, 4-'-diphenylmethane diisocyanate, drip BiCAT8118 catalyzer, add N simultaneously, dinethylformamide and butanone, reaction is until soltion viscosity is 50000mPas, add methyl alcohol end-blocking, namely described use for synthetic leather flame retardant polyurethane resin is obtained after stirring.
Embodiment 5
Raw materials used and the quality of the present embodiment is in table 5.
Table 5
The preparation process of the use for synthetic leather flame retardant polyurethane resin of the present embodiment is as follows:
By BHT, PTMG (number-average molecular weight 2000), poly-hexanodioic acid-1, 4-butanediol ester glycol (number-average molecular weight 2000), ExolitOP550, ExolitOP560, 1, 4-butyleneglycol, the N of 36.5% quality, dinethylformamide drops in reactor together, 45 DEG C stir, add 4, 4-'-diphenylmethane diisocyanate, insulation reaction at 70 DEG C, 4 of surplus are added after 2h, 4-'-diphenylmethane diisocyanate, drip dibutyl tin dilaurate catalyzer, add residue N simultaneously, dinethylformamide and butanone, reaction is until soltion viscosity is 60000mPas, add methyl alcohol end-blocking, namely described use for synthetic leather flame retardant polyurethane resin is obtained after stirring.
Embodiment 6
Raw materials used and the quality of the present embodiment is in table 6.
Table 6
The preparation process of the use for synthetic leather flame retardant polyurethane resin of the present embodiment is as follows:
By antioxidant 1010, PTMG (number-average molecular weight 2000), polyethylene glycol adipate glycol (number-average molecular weight 2000), poly-own Inner esterdiol (number-average molecular weight 2000), ExolitOP560, 1, 4-butyleneglycol, the N of 36.5% quality, dinethylformamide drops in reactor together, 55 DEG C stir, add 4 again, 4-'-diphenylmethane diisocyanate, insulation reaction at 80 DEG C, 4 of surplus are added after 2h, 4-'-diphenylmethane diisocyanate, drip stannous octoate catalyst, add residue N simultaneously, dinethylformamide and ethyl acetate, reaction is until soltion viscosity is 55000mPas, add methyl alcohol end-blocking, namely described use for synthetic leather flame retardant polyurethane resin is obtained after stirring.
Embodiment 7
Raw materials used and the quality of the present embodiment is in table 7.
Table 7
The preparation process of the use for synthetic leather flame retardant polyurethane resin of the present embodiment is as follows:
By BHT, PTMG (number-average molecular weight 2000), polypropylene adipate (PPA) glycol (number-average molecular weight 2000), polybutyleneadipate neopentyl glycol esterdiol (number-average molecular weight 2000), SaytexRB-79, Firemaster520, 1, 4-butyleneglycol, the N of 36.5% quality, dinethylformamide drops in reactor together, 50 DEG C stir, add 4 again, 4-'-diphenylmethane diisocyanate, insulation reaction at 75 DEG C, 4 are added after 2h, 4-'-diphenylmethane diisocyanate, drip BiCAT8118, add remaining N simultaneously, dinethylformamide and butanone, reaction is until soltion viscosity is 35000mPas, add methyl alcohol end-blocking, namely described use for synthetic leather flame retardant polyurethane resin is obtained after stirring.
Embodiment 8
Raw materials used and the quality of the present embodiment is in table 8.
Table 8
The preparation process of the use for synthetic leather flame retardant polyurethane resin of the present embodiment is as follows:
By BHT, PTMG (number-average molecular weight 2000), poly-hexanodioic acid-1, 6-hexylene glycol esterdiol (number-average molecular weight 2000), poly-adipate glycol propylene glycol ester glycol (number-average molecular weight 2000), IXOLM125, IXOLB251, 1, 4-butyleneglycol, the N of 36.5% quality, dinethylformamide drops in reactor together, 55 DEG C stir, add 4 again, 4-'-diphenylmethane diisocyanate and tolylene diisocyanate, insulation reaction at 80 DEG C, 4 are added after 2h, 4-'-diphenylmethane diisocyanate and tolylene diisocyanate, drip BiCAT8118 catalyzer, add remaining N simultaneously, dinethylformamide, butanone and butylacetate reaction are until soltion viscosity is 60000mPas, add methyl alcohol end-blocking, namely described use for synthetic leather flame retardant polyurethane resin is obtained after stirring.
The flame retardant polyurethane resin of embodiment is applied to superfine fiber chemical leather and illustrates:
Respectively by the embodiment resin of 100 parts, the N of 60 parts, dinethylformamide, the butanone of 30 parts, 8 parts of color chips are coated with after mixing and scrape in separate-type paper, and in 130 DEG C of oven for drying, then by commercially available use for synthetic leather tie layer resins, ultra-fine fibre automobile leather base cloth and the fire-retardant surface layer resin after drying are fitted, to dry through roller pressing, finally peel off rolling from separate-type paper, i.e. obtained fire-retardant ultra-fine fibre automobile leather.Embodiment 1 ~ 8 detects in table 9 with the flame retardant properties of common commercially available ultra-fine fibre automobile leather urethane resin sample.
Table 9
As known from Table 9, the ultra-fine fibre automobile leather urethane resin that prepared by the present invention has excellent flame retardant properties.

Claims (9)

1. use for synthetic leather flame retardant polyurethane resin, is characterized in that, is to adopt the component of following mass percent to prepare:
The per-cent sum of each component is 100%.
Described polyvalent alcohol is more than one in polyether glycol or polyester polyol;
The number-average molecular weight of described polyether glycol is 400 ~ 2000; It is 500 ~ 3000 that described polyester polyol is selected from number-average molecular weight; Described flame-proof polyol is functionality is 2, number-average molecular weight be the phosphorus-containing polyol of 100-1000, Halogen polyvalent alcohol one or more.
2. use for synthetic leather flame retardant polyurethane resin according to claim 1, is characterized in that, described polyether glycol is selected from the PTMG that number-average molecular weight is 400 ~ 2000;
Described polyester polyol is selected from the poly-hexanodioic acid-1 that number-average molecular weight is 500 ~ 3000, one or more mixing in 4 butanediol ester glycol, polyethylene glycol adipate glycol, polypropylene adipate (PPA) glycol, poly-hexanodioic acid-1,6 hexylene glycol esterdiol, polyneopentyl glycol adipate glycol, poly-adipate glycol butanediol ester glycol, poly-adipate glycol propylene glycol ester glycol, poly-hexanodioic acid hexylene glycol neopentyl glycol esterdiol, polybutyleneadipate hexylene glycol esterdiol, polybutyleneadipate neopentyl glycol esterdiol, poly-own Inner esterdiol;
Described flame-proof polyol is one or more in ExolitOP550, ExolitOP560, PHT4Diol, SaytexRB-79, Firemaster520, IXOLM125 or IXOLB251.
3. use for synthetic leather flame retardant polyurethane resin according to claim 2, is characterized in that, described polyether glycol is selected from the PTMG that number-average molecular weight is 2000;
Described polyester polyol is selected from the poly-hexanodioic acid-1 that number-average molecular weight is 2000, one or more mixing in 4 butanediol ester glycol, polyethylene glycol adipate glycol, polypropylene adipate (PPA) glycol, poly-hexanodioic acid-1,6 hexylene glycol esterdiol, polyneopentyl glycol adipate glycol, poly-adipate glycol butanediol ester glycol, poly-adipate glycol propylene glycol ester glycol, poly-hexanodioic acid hexylene glycol neopentyl glycol esterdiol, polybutyleneadipate hexylene glycol esterdiol, polybutyleneadipate neopentyl glycol esterdiol, poly-own Inner esterdiol.
4. use for synthetic leather flame retardant polyurethane resin according to claim 1, is characterized in that, described small molecule polyol is C 2-6aliphatic diol one or more.
5. use for synthetic leather flame retardant polyurethane resin according to claim 1, it is characterized in that, described vulcabond is 4,4-'-diphenylmethane diisocyanate MDI, tolylene diisocyanate TDI, tolylene diisocyanate XDI, 1,5-is vulcabond NDI, PPDI PPDI, hexamethylene diisocyanate HDI, hydrogenation 4,4-'-diphenylmethane diisocyanate H how 12one or more in MDI.
6. use for synthetic leather flame retardant polyurethane resin according to claim 1, is characterized in that, described organic solvent is one or more mixing in DMF, N,N-dimethylacetamide, toluene, butanone, vinyl acetic monomer, N-BUTYL ACETATE.
7. use for synthetic leather flame retardant polyurethane resin according to claim 1, it is characterized in that, described terminator is single functionality alcohol, described catalyzer is dibutyl tin dilaurate, stannous octoate or BiCAT8118, and described auxiliary agent is one or more in oxidation inhibitor, flow agent, slipping agent, UV light absorber.
8. the preparation method of the use for synthetic leather flame retardant polyurethane resin according to any one of claim 1 ~ 7, is characterized in that, comprise the steps:
(1) more than one in polyether glycol or polyester polyol, flame-proof polyol, small molecule polyol, part organic solvent and auxiliary agent are mixed, then add di-isocyanate reaction;
(2) and then add vulcabond, catalyzer and residual solvent reaction, add terminator end-blocking, stir, namely obtain described use for synthetic leather flame retardant polyurethane resin.
9. method according to claim 8, it is characterized in that, by more than one in polyether glycol or polyester polyol, flame-proof polyol, small molecule polyol, part organic solvent and and auxiliary agent 45 ~ 55 DEG C of mixing, add vulcabond again, react at 70 ~ 80 DEG C, the reaction times is 2h ~ 4 hour;
Described part organic solvent is 30% ~ 50% of organic solvent total mass;
(2) and then add vulcabond, catalyzer and residual solvent, at 70 ~ 80 DEG C reaction until soltion viscosity is 30000 ~ 60000mPas; Add terminator end-blocking, stir, namely obtain described use for synthetic leather flame retardant polyurethane resin.
CN201510981218.4A 2015-12-23 2015-12-23 Flame-retardant polyurethane resin for synthetic leather and preparation method of flame-retardant polyurethane resin Pending CN105504196A (en)

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CN112226157A (en) * 2018-05-25 2021-01-15 广东尚联新材料科技有限公司 Preparation method of nano fireproof heat-insulating high-transparency high-flexibility paint
CN109400837A (en) * 2018-09-30 2019-03-01 南通紫琅生物医药科技有限公司 A kind of Halogen does not migrate flame retardant polyurethane resin and its application without molten drop
CN110845954A (en) * 2019-11-29 2020-02-28 山东天庆科技发展有限公司 Water-based surface treating agent with flame-retardant effect for synthetic leather and preparation method thereof
CN111204167A (en) * 2020-03-13 2020-05-29 山东轻工职业学院 Method for making waterproof flame-retardant cloth-pasted picture
CN114478989A (en) * 2021-12-30 2022-05-13 兰州大学 Flame-retardant polyurethane and preparation method thereof
CN114478989B (en) * 2021-12-30 2023-08-22 兰州大学 Flame-retardant polyurethane and preparation method thereof

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