CN109280145A - A kind of preparation method of mesoporous modified polyurethane resin - Google Patents

A kind of preparation method of mesoporous modified polyurethane resin Download PDF

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CN109280145A
CN109280145A CN201811112674.5A CN201811112674A CN109280145A CN 109280145 A CN109280145 A CN 109280145A CN 201811112674 A CN201811112674 A CN 201811112674A CN 109280145 A CN109280145 A CN 109280145A
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parts
added
conditions
water
flame retardant
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余旺旺
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Nanjing Institute of Industry Technology
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Nanjing Institute of Industry Technology
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    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
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    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
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Abstract

The invention discloses a kind of preparation methods of mesoporous modified polyurethane resin, including following raw material components: presoma, silane coupling agent, phosphorous acid, 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, new flame retardant, methyl diphenylene diisocyanate, ethylene glycol, 1, 4- butanediol, polyester diol, toluene, N, dinethylformamide, catalyst, methanol, ammonium hydrogen carbonate, presoma is by ammonium silicate, triethylene tetramine and zinc ammonia complex reaction are made, zinc ammonia complex is by zinc sulfate, ammonia and water reaction are made, new flame retardant is by oxalic acid, water and urea reaction are made.Mesoporous material in the invention can be improved the mechanical strength of polyurethane product, increase polyurethane surface degree of functionality and hydrophily, meanwhile, mesoporous material assigns the performances such as excellent transparent, fungi-proofing, the fire-retardant, peel strength of polyurethane, heat-insulated, sound-absorbing.

Description

A kind of preparation method of mesoporous modified polyurethane resin
Technical field
The present invention relates to a kind of preparation methods of mesoporous modified polyurethane resin.
Background technique
Polyurethane resin has the characteristics such as high intensity, tear-proof, wear-resisting, solvent resistant, is widely used in daily life, workers and peasants The fields such as industry production, medicine.Therefore, the synthesis and its application of polyurethane are increasingly taken seriously.
Currently, polyurethane resin is there are fungi-proofing, fire-retardant, peel strength, heat-insulated, sound-absorbing effect is undesirable.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of mesoporous modified polyurethane resin, this method is anti-by changing Answer raw material and processing method, the synthetic leather of mesoporous modified polyurethane resin preparation have fungi-proofing, fire-retardant, peel strength, it is heat-insulated, The performances such as sound-absorbing.
To achieve the goals above, technical scheme is as follows.
A kind of preparation method of mesoporous modified polyurethane resin, it is characterised in that: reacted and be made by following raw material components: is preceding Drive body, silane coupling agent, phosphorous acid, 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, new flame retardant, diphenylmethyl Alkane diisocyanate, ethylene glycol, 1,4- butanediol, polyester diol, toluene, N,N-dimethylformamide, catalyst, methanol, Ammonium hydrogen carbonate, material quality number ratio are 5:0.5~1:0.3~0.8:0.2~0.5:1~5:37~83:7~15:3~10: 100~180:100~200:270~526:0.3~1.6:0.3~0.6:3~8；Wherein, the presoma by ammonium silicate, Triethylene tetramine and zinc ammonia complex reaction are made, and the portion rate of the ammonium silicate, triethylene tetramine and zinc ammonia complex is 10:12~20:50~70；The zinc ammonia complex is reacted by zinc sulfate, ammonia and water to be made, the zinc sulfate, ammonia Portion rate with water is 10:30~60:20~50；The new flame retardant is made by oxalic acid, water and urea reaction, described The portion rate of oxalic acid, water and urea is 100:70~90:60~80.
In the present invention, the silane coupling agent is one kind of propyl trimethoxy silicane, vinyltriethoxysilane Or several mixtures；The catalyst is one of dibutyl tin dilaurate, triethanolamine, stannous octoate；It is described poly- Ester dihydric alcohol is polyethylene glycol adipate dihydric alcohol, polypropylene glycol adipate dihydric alcohol, polyethylene terephthalate two One of first alcohol, polyethylene terephthalate dihydric alcohol.
A kind of preparation method of mesoporous modified polyurethane resin for automobile interiors, it is characterised in that the following steps are included:
It (1), is that 100:70~90:60~80 are added in reactor according to portion rate by oxalic acid, water and urea, stirring speed 130~200r/min is spent, reacts 1~3h under the conditions of 25~46 DEG C of maintenance system temperature, product is through ethanol washing, filtering, 60 DEG C, the dry 2h of -0.1MPa obtains new flame retardant；
(2), it is that 10:30~60:20~50 are added in reactor according to portion rate by zinc sulfate, ammonia and water, stirs 80~150r/min of speed, 0.5~2h is reacted under the conditions of 10~30 DEG C of maintenance system temperature, and -30~-40 DEG C of product warp freezings are dry Dry 1~3h, obtains zinc ammonia complex；While the purpose of the freeze-drying is in order to make zinc ammonia complex rapid draing, drop The volatile quantity of low ammonia.
(3), ammonium silicate, triethylene tetramine and zinc ammonia complex are added to ball according to portion rate 10:12~20:50~70 In type grinder, at 20~30 DEG C of temperature, under the conditions of 100~150r/min 1~3h of griding reaction to get arrive presoma；It is described Triethylene tetramine purpose on the one hand, for better disperse silicic acid ammonium and zinc ammonia complex；On the other hand, it is situated between to modify Porous materials surface.
(4), presoma, silane coupling agent, phosphorous acid, 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, novel resistance Fire agent, methyl diphenylene diisocyanate, ethylene glycol, 1,4- butanediol, polyester diol, toluene, N,N-dimethylformamide, Catalyst, methanol, ammonium hydrogen carbonate are according to portion rate 5:0.5~1:0.3~0.8:0.2~0.5:1~5:37~83:7~15:3 ~10:100~180:100~200:270~526:0.3~1.6:0.3~0.6:3~8 are added in reaction kettle, in temperature 65 ~80 DEG C, 1~3h is reacted under the conditions of 90~130r/min to get mesoporous material modified polyurethane resin is arrived.
Invention has the beneficial effects that:
1, ammonium silicate and zinc ammonia complex be in polyurethane synthesis process while available preferable mixing, ammonium silicate and Zinc ammonia complex, which can decompose, generates nano silica and nano zine oxide, and the two is divided well in polyurethane body body It dissipates, improves agglomeration of the mesoporous material in polyurethane.Also, the ammonia generated in ammonium silicate and zinc ammonia complex decomposable process As pore creating material during nano silica and zinc oxide generate, the silica and zinc oxide for assigning generation are mesoporous Silica and mesoporous zinc oxide；
2, in the synthesis process due to mesoporous silicon oxide and mesoporous zinc oxide, there is ammonia generation, ammonia and organic amine can To modify newly-generated mesoporous material surface, amine (ammonia) modified mesoporous material is obtained；
3, in polyurethane synthesis process, raising of the ammonium carbonate with reaction temperature, reaction of decomposing generates titanium dioxide Carbon, water, ammonia, these substances can play the role of the foaming agent of polyurethane, assign the excellent elasticity of polyurethane resin, sound-absorbing Performance；
4, when polyurethane is under combustion state, on the one hand, phosphorous acid can consume oxygen as reducing agent；Another party Face, amine (ammonia) modified mesoporous material can be migrated to polyurethane surface, polycondensation reaction occur with (Asia) phosphoric acid, in polyurethane surface shape At one layer of flame-retardant layer；
5, when polyurethane is in combustion state, one side oxalic acid-urea fire retardant is thermally decomposed to generate carbon dioxide, ammonia Etc. non-combustion-supporting property gas, on the other hand, polymerization reaction can occur at high temperature for oxalic acid-urea fire retardant, in polyurethane surface shape At one layer of flame-retardant layer；
6, mesoporous silicon oxide and zinc oxide introduce, and due to crazing effect, improve the mechanical property of modified polyurethane.
The invention uses presoma, new flame retardant, methyl diphenylene diisocyanate, ethylene glycol, 1,4- butanediol, gathers The raw materials such as ester dihydric alcohol, ammonium hydrogen carbonate are prepared for having the advantages such as excellent fungi-proofing, fire-retardant, peel strength, heat-insulated, sound-absorbing effect Mesoporous modified polyurethane resin for automobile interiors.
The present invention can be improved the mechanical strength of polyurethane product, increase polyurethane surface degree of functionality and hydrophily, meanwhile, Mesoporous material assigns the performances such as excellent transparent, fungi-proofing, the fire-retardant, peel strength of polyurethane, heat-insulated, sound-absorbing.
The present invention can apply strong in automobile, building, sofa, household outer packing, luggage, the fungi-proofing, fire-retardant of fur clothing, removing The fields such as degree, heat-insulated, sound-absorbing.
Specific embodiment
A specific embodiment of the invention is described below with reference to embodiment, to better understand the present invention.
Embodiment 1
(1), 100 parts of oxalic acid, 82 parts of water and 67 parts of urea are weighed to be added in reactor, mixing speed 165r/min, is tieed up React 2h under the conditions of holding 30 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa obtains To new flame retardant；
(2), 10 parts of zinc sulfate, 45 parts of ammonias and 39 parts of water are weighed to be added in reactor, mixing speed 120r/min, is tieed up 1h is reacted under the conditions of holding 26 DEG C of system temperature, -35 DEG C of freeze-drying 2h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 16 parts of triethylene tetramines and 65 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 26 DEG C of temperature, under the conditions of 130r/min griding reaction 2h to get arrive presoma；
(4), 5 parts of presomas, 0.8 part of (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 0.5 part of phosphorous acid, 0.3 are weighed Part 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, 3.5 parts of new flame retardant, 67 parts of methyl diphenylene diisocyanates, 12 parts of ethylene glycol, 7 parts of 1,4- butanediols, 150 parts of polypropylene glycol adipate dihydric alcohols, 155 parts of toluene, 440 parts of N, N- diformazan Base formamide, 0.9 part of dibutyl tin dilaurate, 0.6 part of methanol, 5 parts of ammonium hydrogen carbonate are added in reaction kettle, in temperature 70 DEG C, 2h is reacted under the conditions of 110r/min to get mesoporous material modified polyurethane resin is arrived.Table 1 is in automobile made from embodiment 1 Adorn the performance parameter of mesoporous modified polyurethane resin.
Embodiment 2
(1), 100 parts of oxalic acid, 70 parts of water and 60 parts of urea are weighed to be added in reactor, mixing speed 130r/min, is tieed up React 1h under the conditions of holding 25 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa obtains To new flame retardant；
(2), 10 parts of zinc sulfate, 30 parts of ammonias and 20 parts of water are weighed to be added in reactor, mixing speed 80r/min, is tieed up 0.5h is reacted under the conditions of holding 10 DEG C of system temperature, -30 DEG C of freeze-drying 1h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 12 parts of triethylene tetramines and 50 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 20 DEG C of temperature, under the conditions of 100r/min griding reaction 1h to get arrive presoma；
(4), 5 parts of presomas, 0.5 part of vinyltriethoxysilane, 0.3 part of phosphorous acid, 0.2 part of 2- (2 ˊ-hydroxyl are weighed - 5 ˊ of base-aminomethyl phenyl) benzotriazole, 1 part of new flame retardant, 37 parts of methyl diphenylene diisocyanates, 7 parts of ethylene glycol, 3 Part 1,4- butanediol, 100 parts of polyethylene terephthalate dihydric alcohols, 100 parts of toluene, 270 parts of N,N-dimethylformamides, 0.3 part of triethanolamine, 0.3 part of methanol, 3 parts of ammonium hydrogen carbonate are added in reaction kettle, anti-under the conditions of 90r/min at 65 DEG C of temperature 1h is answered to get mesoporous material modified polyurethane resin is arrived.
Embodiment 3
(1), 100 parts of oxalic acid, 90 parts of water and 80 parts of urea are weighed to be added in reactor, mixing speed 200r/min, is tieed up React 3h under the conditions of holding 46 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa obtains To new flame retardant；
(2), 10 parts of zinc sulfate, 60 parts of ammonias and 50 parts of water are weighed to be added in reactor, mixing speed 150r/min, is tieed up 2h is reacted under the conditions of holding 30 DEG C of system temperature, -40 DEG C of freeze-drying 3h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 20 parts of triethylene tetramines and 70 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 30 DEG C of temperature, under the conditions of 150r/min griding reaction 3h to get arrive presoma；
(4), weigh 5 parts of presomas, 1 part of (methacryloxypropyl) propyl trimethoxy silicane, 0.8 part of phosphorous acid, 0.2~ 0.5 part of 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, 5 parts of new flame retardant, 83 parts of diphenylmethane diisocyanates Ester, 15 parts of ethylene glycol, 10 parts of 1,4- butanediols, 180 parts of polypropylene glycol adipate dihydric alcohols, 200 parts of toluene, 526 parts of N, N- Dimethylformamide, 1.6 parts of dibutyl tin dilaurates, 0.6 part of methanol, 8 parts of ammonium hydrogen carbonate are added in reaction kettle, in temperature 80 DEG C, 3h is reacted under the conditions of 130r/min to get mesoporous material modified polyurethane resin is arrived.
Embodiment 4
(1), 100 parts of oxalic acid, 73 parts of water and 66 parts of urea are weighed to be added in reactor, mixing speed 137r/min, is tieed up React 3h under the conditions of holding 28 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa obtains To new flame retardant；
(2), 10 parts of zinc sulfate, 35 parts of ammonias and 28 parts of water are weighed to be added in reactor, mixing speed 85r/min, is tieed up 0.8h is reacted under the conditions of holding 13 DEG C of system temperature, -35 DEG C of freeze-drying 1h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 15 parts of triethylene tetramines and 58 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 23 DEG C of temperature, under the conditions of 110r/min griding reaction 3h to get arrive presoma；
(4), 5 parts of presomas, 0.7 part of vinyltriethoxysilane, 0.8 part of phosphorous acid, 0.3 part of 2- (2 ˊ-hydroxyl are weighed - 5 ˊ of base-aminomethyl phenyl) benzotriazole, 2 parts of new flame retardant, 56 parts of methyl diphenylene diisocyanates, 8 parts of ethylene glycol, 9 Part 1,4- butanediol, 100 parts of polyethylene terephthalate dihydric alcohols, 120 parts of toluene, 326 parts of N,N-dimethylformamides, 0.7 part of triethanolamine, 0.5 part of methanol, 6 parts of ammonium hydrogen carbonate are added in reaction kettle, anti-under the conditions of 100r/min at 68 DEG C of temperature 1.5h is answered to get mesoporous material modified polyurethane resin is arrived.
Embodiment 5
(1), 100 parts of oxalic acid, 75 parts of water and 67 parts of urea are weighed to be added in reactor, mixing speed 146r/min, is tieed up React 2h under the conditions of holding 30 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa obtains To new flame retardant；
(2), 10 parts of zinc sulfate, 33 parts of ammonias and 22 parts of water are weighed to be added in reactor, mixing speed 90r/min, is tieed up 1.2h is reacted under the conditions of holding 18 DEG C of system temperature, -33 DEG C of freeze-drying 2h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 15 parts of triethylene tetramines and 57 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 26 DEG C of temperature, under the conditions of 130r/min griding reaction 2h to get arrive presoma；
(4), 5 parts of presomas, 0.7 part of (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 0.6 part of phosphorous acid, 0.4 are weighed Part 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, 4 parts of new flame retardant, 80 parts of methyl diphenylene diisocyanates, 14 Part ethylene glycol, 7 parts of 1,4- butanediols, 160 parts of polypropylene glycol adipate dihydric alcohols, 180 parts of toluene, 470 parts of N, N- dimethyl Formamide, 1.4 parts of stannous octoates, 0.5 part of methanol, 4 parts of ammonium hydrogen carbonate are added in reaction kettle, at 71 DEG C of temperature, 96r/min item 2h is reacted under part to get mesoporous material modified polyurethane resin is arrived.
Embodiment 6
(1), 100 parts of oxalic acid, 80 parts of water and 76 parts of urea are weighed to be added in reactor, mixing speed 150r/min, is tieed up React 1h under the conditions of holding 45 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa obtains To new flame retardant；
(2), 10 parts of zinc sulfate, 58 parts of ammonias and 49 parts of water are weighed to be added in reactor, mixing speed 147r/min, is tieed up 1.8h is reacted under the conditions of holding 28 DEG C of system temperature, -39 DEG C of freeze-drying 2h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 17 parts of triethylene tetramines and 66 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 24 DEG C of temperature, under the conditions of 130r/min griding reaction 2h to get arrive presoma；
(4), 5 parts of presomas, 0.8 part of vinyltriethoxysilane, 0.6 part of phosphorous acid, 0.4 part of 2- (2 ˊ-hydroxyl are weighed - 5 ˊ of base-aminomethyl phenyl) benzotriazole, 3 parts of new flame retardant, 60 parts of methyl diphenylene diisocyanates, 9 parts of ethylene glycol, 5 Part 1,4- butanediol, 160 parts of polyethylene glycol adipate dihydric alcohols, 170 parts of toluene, 326 parts of N,N-dimethylformamides, 1.6 Part dibutyl tin dilaurate, 0.5 part of methanol, 6 parts of ammonium hydrogen carbonate are added in reaction kettle, at 73 DEG C of temperature, 123r/min item 2h is reacted under part to get mesoporous material modified polyurethane resin is arrived.
Embodiment 7
(1), 100 parts of oxalic acid, 84 parts of water and 73 parts of urea are weighed to be added in reactor, mixing speed 150r/min, is tieed up React 2.5h under the conditions of holding 37 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa, Obtain new flame retardant；
(2), 10 parts of zinc sulfate, 53 parts of ammonias and 46 parts of water are weighed to be added in reactor, mixing speed 120r/min, is tieed up 1.7h is reacted under the conditions of holding 26 DEG C of system temperature, -37 DEG C of freeze-drying 2.5h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 17 parts of triethylene tetramines and 66 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 21 DEG C of temperature, under the conditions of 124r/min griding reaction 2.8h to get arrive presoma；
(4), 5 parts of presomas, 0.8 part of (methacryloxypropyl) propyl trimethoxy silicane, 0.6 part of phosphorous acid, 0.4 are weighed Part 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, 3 parts of new flame retardant, 41 parts of methyl diphenylene diisocyanates, 7 Part ethylene glycol, 8 parts of 1,4- butanediols, 140 parts of polyethylene terephthalate dihydric alcohols, 100 parts of toluene, 270 parts of N, N- diformazan Base formamide, 1.6 parts of stannous octoates, 0.3 part of methanol, 3 parts of ammonium hydrogen carbonate are added in reaction kettle, at 76 DEG C of temperature, 110r/ 1h is reacted under the conditions of min to get mesoporous material modified polyurethane resin is arrived.
Embodiment 8
(1), 100 parts of oxalic acid, 83 parts of water and 75 parts of urea are weighed to be added in reactor, mixing speed 170r/min, is tieed up React 1.7h under the conditions of holding 34 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa, Obtain new flame retardant；
(2), 10 parts of zinc sulfate, 48 parts of ammonias and 44 parts of water are weighed to be added in reactor, mixing speed 116r/min, is tieed up 1.3h is reacted under the conditions of holding 27 DEG C of system temperature, -32 DEG C of freeze-drying 3h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 15 parts of triethylene tetramines and 65 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 26 DEG C of temperature, under the conditions of 130r/min griding reaction 2h to get arrive presoma；
(4), 5 parts of presomas, 0.7 part of vinyltriethoxysilane, 0.7 part of phosphorous acid, 0.4 part of 2- (2 ˊ-hydroxyl are weighed - 5 ˊ of base-aminomethyl phenyl) benzotriazole, 4 parts of new flame retardant, 72 parts of methyl diphenylene diisocyanates, 9 parts of ethylene glycol, 6 Part 1,4- butanediol, 158 parts of polyethylene glycol adipate dihydric alcohols, 130 parts of toluene, 430 parts of N,N-dimethylformamides, 1.5 Part dibutyl tin dilaurate, 0.4 part of methanol, 5 parts of ammonium hydrogen carbonate are added in reaction kettle, at 73 DEG C of temperature, 126r/min item 2.3h is reacted under part to get mesoporous material modified polyurethane resin is arrived.
Embodiment 9
(1), 100 parts of oxalic acid, 81 parts of water and 77 parts of urea are weighed to be added in reactor, mixing speed 180r/min, is tieed up React 2h under the conditions of holding 29 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa obtains To new flame retardant；
(2), 10 parts of zinc sulfate, 36 parts of ammonias and 40 parts of water are weighed to be added in reactor, mixing speed 130r/min, is tieed up 1.9h is reacted under the conditions of holding 17 DEG C of system temperature, -38 DEG C of freeze-drying 1.5h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 17 parts of triethylene tetramines and 63 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 26 DEG C of temperature, under the conditions of 130r/min griding reaction 2h to get arrive presoma；
(4), 5 parts of presomas, 0.7 part of (methacryloxypropyl) propyl trimethoxy silicane, 0.5 part of phosphorous acid, 0.3 are weighed Part 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, 4 parts of new flame retardant, 67 parts of methyl diphenylene diisocyanates, 12 Part ethylene glycol, 7 parts of 1,4- butanediols, 180 parts of polyethylene terephthalate dihydric alcohols, 180 parts of toluene, 390 parts of N, N- diformazan Base formamide, 1.3 parts of stannous octoates, 0.4 part of methanol, 5 parts of ammonium hydrogen carbonate are added in reaction kettle, at 73 DEG C of temperature, 111r/ 2.6h is reacted under the conditions of min to get mesoporous material modified polyurethane resin is arrived.
Embodiment 10
(1), 100 parts of oxalic acid, 82 parts of water and 71 parts of urea are weighed to be added in reactor, mixing speed 180r/min, is tieed up React 2.3h under the conditions of holding 43 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa, Obtain new flame retardant；
(2), 10 parts of zinc sulfate, 41 parts of ammonias and 44 parts of water are weighed to be added in reactor, mixing speed 134r/min, is tieed up 1.7h is reacted under the conditions of holding 16 DEG C of system temperature, -38 DEG C of freeze-drying 2.3h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 14 parts of triethylene tetramines and 63 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 22 DEG C of temperature, under the conditions of 140r/min griding reaction 2.3h to get arrive presoma；
(4), 5 parts of presomas, 0.7 part of (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 0.6 part of phosphorous acid, 0.5 are weighed Part 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, 3 parts of new flame retardant, 63 parts of methyl diphenylene diisocyanates, 9 Part ethylene glycol, 9 parts of 1,4- butanediols, 150 parts of polyethylene glycol adipate dihydric alcohols, 170 parts of toluene, 350 parts of N, N- dimethyl Formamide, 1.5 parts of dibutyl tin dilaurates, 0.4 part of methanol, 4 parts of ammonium hydrogen carbonate are added in reaction kettle, at 77 DEG C of temperature, 2h is reacted under the conditions of 123r/min to get mesoporous material modified polyurethane resin is arrived.
Embodiment 11
(1), 100 parts of oxalic acid, 89 parts of water and 75 parts of urea are weighed to be added in reactor, mixing speed 190r/min, is tieed up React 2h under the conditions of holding 37 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa obtains To new flame retardant；
(2), 10 parts of zinc sulfate, 40 parts of ammonias and 41 parts of water are weighed to be added in reactor, mixing speed 86r/min, is tieed up 1.8h is reacted under the conditions of holding 23 DEG C of system temperature, -36 DEG C of freeze-drying 1h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 14 parts of triethylene tetramines and 60 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 29 DEG C of temperature, under the conditions of 135r/min griding reaction 2h to get arrive presoma；
(4), 5 parts of presomas, 0.7 part of (methacryloxypropyl) propyl trimethoxy silicane, 0.6 part of phosphorous acid, 0.3 are weighed Part 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, 4 parts of new flame retardant, 46 parts of methyl diphenylene diisocyanates, 7 Part ethylene glycol, 3 parts of 1,4- butanediols, 110 parts of polyethylene terephthalate dihydric alcohols, 100 parts of toluene, 300 parts of N, N- diformazan Base formamide, 1.5 parts of stannous octoates, 0.6 part of methanol, 5 parts of ammonium hydrogen carbonate are added in reaction kettle, at 75 DEG C of temperature, 97r/min Under the conditions of reaction 2h to get arrive mesoporous material modified polyurethane resin.
Embodiment 12
(1), 100 parts of oxalic acid, 81 parts of water and 72 parts of urea are weighed to be added in reactor, mixing speed 170r/min, is tieed up React 1.5h under the conditions of holding 30 DEG C of system temperature, product through 500mL ethanol washing twice, filtering, 60 DEG C, the dry 2h of -0.1MPa, Obtain new flame retardant；
(2), 10 parts of zinc sulfate, 35 parts of ammonias and 21 parts of water are weighed to be added in reactor, mixing speed 88r/min, is tieed up 1.5h is reacted under the conditions of holding 18 DEG C of system temperature, -34 DEG C of freeze-drying 1h of product warp obtain zinc ammonia complex；
(3), 10 parts of ammonium silicates, 16 parts of triethylene tetramines and 57 parts of zinc ammonia complex are weighed to be added in ball-type grinder, At 25 DEG C of temperature, under the conditions of 140r/min griding reaction 3h to get arrive presoma；
(4), 5 parts of presomas, 0.7 part of (the third oxygen of 2,3- epoxy) propyl trimethoxy silicane, 0.4 part of phosphorous acid, 0.2 are weighed Part 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, 3 parts of new flame retardant, 50 parts of methyl diphenylene diisocyanates, 7 Part ethylene glycol, 4 parts of 1,4- butanediols, 120 parts of polyethylene terephthalate dihydric alcohols, 130 parts of toluene, 270 parts of N, N- diformazan Base formamide, 0.7 part of dibutyl tin dilaurate, 0.5 part of methanol, 8 parts of ammonium hydrogen carbonate are added in reaction kettle, in temperature 74 DEG C, 1.5h is reacted under the conditions of 117r/min to get mesoporous material modified polyurethane resin is arrived.
The performance parameter of mesoporous modified polyurethane synthetic leather resin for automobile interiors made from 1 embodiment 1 of table
The above is the preferred embodiment of the invention, it is noted that for those skilled in the art For, under the premise of not departing from the inventive principle, several improvements and modifications can also be made, these improvements and modifications are also considered as The protection scope of the invention.

Claims (2)

1. a kind of preparation method of mesoporous modified polyurethane resin, it is characterised in that: reacted and be made by following raw material components: forerunner Body, silane coupling agent, phosphorous acid, 2- (- 5 ˊ of 2 ˊ-hydroxyl-aminomethyl phenyl) benzotriazole, new flame retardant, diphenyl methane Diisocyanate, ethylene glycol, 1,4- butanediol, polyester diol, toluene, N,N-dimethylformamide, catalyst, methanol, carbon Sour hydrogen ammonium, material quality number ratio are 5:0.5~1:0.3~0.8:0.2~0.5:1~5:37~83:7~15:3~10:100 ~180:100~200:270~526:0.3~1.6:0.3~0.6:3~8；Wherein, the presoma is by ammonium silicate, three second Alkene tetramine and zinc ammonia complex reaction are made, and the portion rate of the ammonium silicate, triethylene tetramine and zinc ammonia complex is 10:12 ~20:50~70 are added in ball-type grinder, at 20~30 DEG C of temperature, griding reaction 1 under the conditions of 100~150r/min~ 3h；The zinc ammonia complex is reacted by zinc sulfate, ammonia and water to be made, and the portion rate of the zinc sulfate, ammonia and water is 10:30~60:20~50 are added in reactor, 80~150r/min of mixing speed, 10~30 DEG C of conditions of maintenance system temperature 0.5~2h of lower reaction, -30~-40 DEG C of 1~3h of freeze-drying of product warp；The new flame retardant is anti-by oxalic acid, water and urea It should be made, the portion rate of the oxalic acid, water and urea is that 100:70~90:60~80 are added in reactor, mixing speed 130~200r/min, reacts 1~3h under the conditions of 25~46 DEG C of maintenance system temperature, product through ethanol washing, filtering, 60 DEG C ,- 0.1MPa dries 2h.
2. a kind of preparation method of mesoporous modified polyurethane resin according to claim 1, it is characterised in that: Jie Porous materials modified polyurethane resin is as made from following preparation method: by presoma, silane coupling agent, phosphorous acid, 2- (2 ˊ- - 5 ˊ of hydroxyl-aminomethyl phenyl) benzotriazole, new flame retardant, methyl diphenylene diisocyanate, ethylene glycol, 1,4- fourth two Alcohol, polyester diol, toluene, N,N-dimethylformamide, catalyst, methanol, ammonium hydrogen carbonate are according to portion rate 5:0.7~0.8: 0.5~0.7:0.3~0.4:2~4:56~80:8~14:5~9:140~160:120~180:326~470:0.7~1.4: 0.4~0.5:4~6 are added in reaction kettle, and at 68~73 DEG C of temperature, 1.5~2h is reacted under the conditions of 96~123r/min.
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Application publication date: 20190129