CN104987493B - Siliceous boracic aqueous polyurethane and preparation method thereof - Google Patents

Siliceous boracic aqueous polyurethane and preparation method thereof Download PDF

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CN104987493B
CN104987493B CN201510353859.5A CN201510353859A CN104987493B CN 104987493 B CN104987493 B CN 104987493B CN 201510353859 A CN201510353859 A CN 201510353859A CN 104987493 B CN104987493 B CN 104987493B
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aqueous polyurethane
siliceous
boracic
mol ratio
dmpa
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CN104987493A (en
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徐文总
聂祝婷
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Anhui Jinyue Hengtong Transportation Equipment Co.,Ltd.
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Anhui Jianzhu University
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Abstract

The primary and foremost purpose of the present invention is to provide a kind of siliceous boracic aqueous polyurethane, and another object of the present invention is to provide a kind of preparation method of above-mentioned siliceous boracic aqueous polyurethane, comprised the following steps：A, macromolecule dihydric alcohol is weighed to mix with TDI; 70~90 DEG C are warming up under N2 protections; react 1~3h; then first add DMPA and react 1~2h; add BDO and react 1~3h, be cooled to 60~70 DEG C, amino-terminated 0.5~1.5h of siloxane reactions is then added dropwise; 30~50 DEG C are cooled to, obtains the polyurethane of siloxane blocking；B, the polyurethane of siloxane blocking is placed under 1500~2000rpm speed conditions, TEA is first added to be emulsified, neutralize 20~30min, add boric acid and continue 10~20min of emulsification, be evaporated under reduced pressure, obtain the siliceous boracic aqueous polyurethane that solid content is 25~35%.The aqueous polyurethane that the present invention is prepared not only while has good hydrophobic, fire-retardant and smoke suppressing, and the mechanical property of material can be effectively ensured in actual applications.

Description

Siliceous boracic aqueous polyurethane and preparation method thereof
Technical field
The present invention relates to technical field of chemistry, and in particular to a kind of siliceous boracic aqueous polyurethane and preparation method thereof.
Background technology
At present, aqueous polyurethane has been widely used in the processing of the products such as coating, adhesive and leather, but existing The aqueous polyurethane that the present is commonly used contains hydrophilic radical, and its film does not have hydrophobicity, in addition, the film of aqueous polyurethane easily burns, Not only poor flame retardant properties, and more smog is also frequently accompanied by during burning and is produced, these defects undoubtedly limit water-based poly- ammonia The practical application of ester.
It is well known that silicon-containing compound has excellent hydrophobic performance, such as, Chinese periodical《Organosilicon material》2012 Year volume 26 the 1st is interim《The synthesis of hydroxyethyl-terminapolydimethylsiloxanewaterborne polydimethylsiloxanewaterborne waterborne polyurethane》One the article pointed out it is cloudy from The organic-silicon-modified aqueous polyurethane of subtype can effectively improve the hydrophobicity of material；Chinese periodical《Printing and dyeing assistant》2015 Volume 32 the 1st is interim《The preparation of hydroxypropyl terminated polysiloxane modified aqueous polyurethane and its performance study》One the article pointed out Hydroxypropyl terminated polysiloxane modified aqueous polyurethane emulsion can improve the hydrophobicity of material.Pass through these data informations Researcher is not difficult to learn, aqueous polyurethane can be improved in theory by silicon-containing compound being incorporated into aqueous polyurethane segment The hydrophobicity of glued membrane, but how reliably to introduce silicon-containing compound, this or a technical barrier.Have in addition, boron is one kind Fire-retardant, suppression hood element, boron-containing compound is directly appended to improve the fire-retardant of material in water-base polyurethane material Smoke suppressing, but find so reduce the mechanical property of water-base polyurethane material during practical application.In general, city at present Had not been reported on field while there is good hydrophobic, fire-retardant and smoke suppressing aqueous polyurethane.
The content of the invention
The primary and foremost purpose of the present invention is to provide a kind of while has good hydrophobic, fire-retardant and smoke suppressing siliceous contain Boron aqueous polyurethane.
To achieve the above object, the technical solution adopted by the present invention is：1st, a kind of siliceous boracic aqueous polyurethane, its feature It is：The chemical structural formula of the aqueous polyurethane is as follows：
Wherein-R- structure is：-CH2CH2CH2-、-CH2CH2NHCH2CH2CH2- or- CH2CH2NHCH2CH2NHCH2CH2CH2-；
-R1- structure be：
-R2- structure be：
N in structural formula is the arbitrary integer more than zero, and m is the integer between 1~30.
Another object of the present invention is to provide a kind of preparation method of siliceous boracic aqueous polyurethane as described above, Comprise the following steps：
A, by 1：2.2~3.0 mol ratio weighs macromolecule dihydric alcohol and mixed with TDI (i.e. toluene di-isocyanate(TDI)), N270~90 DEG C are warming up under protection, reacts 1~3h, DMPA (i.e. 2,2- dihydromethyl propionic acids) is then first added and reacts 1~2h, Add BDO (i.e. BDO) and react 1~3h, be cooled to 60~70 DEG C, amino-terminated siloxane reactions are then added dropwise 0.5~1.5h, 30~50 DEG C are cooled to, obtain the polyurethane of siloxane blocking, acetone regulation system viscosity is added dropwise in course of reaction, The DMPA, BDO, amino-terminated siloxanes and TDI mol ratio are respectively 0.2~0.4:0.1~0.5:0.03~ 0.23:1, described macromolecule dihydric alcohol is polyester diol or polyether Glycols, and the quality addition of described acetone is big The 50-150% of molecule dihydric alcohol quality；
B, the polyurethane of siloxane blocking is placed under 1500~2000rpm speed conditions, first adds TEA and carry out breast Change, neutralize 20~30min, add boric acid and continue 10~20min of emulsification, be evaporated under reduced pressure, it is 25~35% to contain to obtain solid content Silicon boracic aqueous polyurethane, the mol ratio of the TEA and DMPA are 0.8~1:1, boron element and amino-terminated silicon in boric acid The mol ratio of element silicon in oxygen alkane is 2~3:1.
Siliceous boracic aqueous polyurethane disclosed by the invention is a kind of novel aqueous polyurethane, with existing aqueous polyurethane Compare, it has the advantages of the following aspects：Firstth, the surface tension of silicon-containing compound is small, and the oriented glued membrane of silicon-containing group The tendency of surface enrichment, so that the hydrophobic performance of siliceous boracic water-base polyurethane material is higher than conventional aqueous polyurethane material Material；Secondth, boron is a kind of fire-retardant, suppression hood element, and boron-containing compound can melt the thing to form similar glassy state when burning Matter and the surface for being covered in siliceous boracic water-base polyurethane material, so can not only avoid material further degrade produce it is flammable Property gas, reduce the generation of flammable effusion thing, and can increase material into carbon amounts, so as to completely cut off the oxygen in air, And then effectively improve fire-retardant, the smoke suppressing of material.Compared with prior art, the present invention by chemical method by silicon, boron element It is incorporated into polyurethane segment, there can not be hydrophobic, fire-retardant and smoke suppressing simultaneously after overcoming current aqueous polyurethane film forming The shortcomings that, in addition, prior art mainly improves material flame retarding and smoke suppressing properties using addition anti-flaming smoke-inhibiting agent in the material, but It is the mechanical properties decrease that can so cause material, by comparison, is contained using what polymerization disclosed by the invention was prepared Silicon boracic aqueous polyurethane, it is not only hydrophobic, flame retarding and smoke suppressing properties are good, and material can be effectively ensured in actual applications Mechanical property.
Specifically, the macromolecule dihydric alcohol in the step a is PPOX ether dihydric alcohol, PTMG binary Alcohol or polyethylene glycol adipate glycol；Amino-terminated siloxanes in the step a is 3- aminopropyl triethoxysilanes, N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes or diethylenetriamine base propyl trimethoxy silicane.
Applicant is verified by substantial amounts of experimental study and found, as further preferred scheme：The step a is by 1: 2.6 mol ratio weighs macromolecule dihydric alcohol and mixed with TDI, in N280 DEG C are warming up under protection, 2h is reacted, then first adds DMPA reacts 1.5h, adds BDO reaction 2h, is cooled to 65 DEG C, and amino-terminated siloxanes is then added dropwise and continues to react 1h, drop Temperature obtains the polyurethane of siloxane blocking, the DMPA, BDO, amino-terminated siloxanes and TDI mol ratio are to 40 DEG C 0.28:0.23:0.21:1, the siliceous boracic aqueous polyurethane for be prepared using above-mentioned parameter condition it is hydrophobic, fire-retardant And smoke suppressing is optimal, and during practical application material mechanical property it is good.
During preparing siliceous boracic aqueous polyurethane using method disclosed by the invention, in order to be further ensured that preparation work Skill, it is preferable that acetone is added dropwise into reactant with regulation system viscosity, the dropwise addition of acetone in step a whole course of reaction Quality is the 100%~150% of macromolecule dihydric alcohol quality.The addition of acetone can be reduced in step a whole course of reaction The viscosity of reactant, and then ensure that reaction raw materials are sufficiently mixed, make reaction complete.Further, the TEA and DMPA Mol ratio is 0.9:1；The mol ratio of boron element in the boric acid and the element silicon in amino-terminated siloxanes is 2:1.
Embodiment
1-4 is further described to technical scheme disclosed by the invention with reference to embodiments：
Embodiment 1：The preparation of siliceous boracic aqueous polyurethane
1) 1 is pressed:2.2 mol ratio weighs the polyethylene glycol adipate glycol that mean molecule quantity is 1000 and TDI and added Enter into four dry neck round-bottom flasks, in N280 DEG C are warming up under protection, reacts 2h, then first adds DMPA reaction 1h, then Add BDO and carry out chain extending reaction 2h, be cooled to 60 DEG C, 3- aminopropyl triethoxysilanes reaction 0.5h is then added dropwise, is cooled to 40 DEG C, the polyurethane of siloxane blocking is obtained, acetone regulation system viscosity, DMPA, BDO, 3- ammonia third is added dropwise in course of reaction Ethyl triethoxy silicane alkane and TDI mol ratio are 0.23:0.27:0.08:1, the quality addition of described acetone is to gather oneself The 150% of naphthalate glycol quality；
2) polyurethane for the siloxane blocking for synthesizing step 1 is placed under 1500rpm speed conditions, is first added TEA and is entered Row emulsification, neutralize 20min, add boric acid continue emulsify 20min, be evaporated under reduced pressure desolventizing, obtain solid content be 25% it is siliceous Boracic aqueous polyurethane, the mol ratio of the TEA and DMPA are 0.8:1, boron element and amino-terminated siloxanes in boric acid In element silicon mol ratio be 2:1；
3) the siliceous boracic aqueous polyurethane that appropriate step 2 is prepared is weighed, is poured into mould, then first in room temperature Under the conditions of stand to surface glued membrane dry, place into baking oven and dry 2h under conditions of 120 DEG C, obtain sample 1, it is to be measured.
Embodiment 2：The preparation of siliceous boracic aqueous polyurethane
1) 1 is pressed:2.6 mol ratio weighs PTMG dihydric alcohol and the TDI that mean molecule quantity is 2000 and added Into four dry neck round-bottom flasks, in N290 DEG C are warming up under protection, reacts 1h, then first adds DMPA reaction 1.5h, then Add BDO and carry out chain extending reaction 3h, be cooled to 70 DEG C, it is anti-that N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes are then added dropwise 1.5h is answered, is cooled to 50 DEG C, obtains the polyurethane of siloxane blocking, acetone regulation system viscosity is added dropwise in course of reaction, it is described DMPA, BDO, N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes and TDI mol ratio are respectively 0.28:0.23: 0.21:1, the quality addition of described acetone is the 150% of PTMG dihydric alcohol quality；
2) polyurethane for the siloxane blocking for synthesizing step 1 is placed under 1700rpm speed conditions, is first added TEA and is entered Row emulsification, neutralize 30min, add boric acid continue emulsify 10min, be evaporated under reduced pressure desolventizing, obtain solid content be 30% it is siliceous Boracic aqueous polyurethane, the mol ratio of the TEA and DMPA are 0.9:1, boron element and amino-terminated siloxanes in boric acid In element silicon mol ratio be 2.5:1；
3) the siliceous boracic aqueous polyurethane that appropriate step 2 is prepared is weighed, is poured into mould, then first in room temperature Under the conditions of stand to surface glued membrane dry, place into baking oven and dry 3h under conditions of 110 DEG C, obtain sample 2, it is to be measured.
Embodiment 3：The preparation of siliceous boracic aqueous polyurethane
1) 1 is pressed:3 mol ratio weighs PPOX ether dihydric alcohol and the TDI that mean molecule quantity is 1750 and is added to In four dry neck round-bottom flasks, in N270 DEG C are warming up under protection, reacts 3h, DMPA reaction 2h is then first added, adds BDO carries out chain extending reaction 1h, is cooled to 65 DEG C, and diethylenetriamine base propyl trimethoxy silicane reaction 0.5h, drop is then added dropwise Temperature obtains the polyurethane of siloxane blocking, acetone regulation system viscosity, the DMPA, divinyl is added dropwise in course of reaction to 40 DEG C Three aminocarbonyl propyl trimethoxy silanes and TDI mol ratio are 0.34:0.25:0.15:1, the quality addition of described acetone Measure as the 100% of PPOX ether dihydric alcohol quality；
2) polyurethane for the siloxane blocking for synthesizing step 1 is placed under 2000rpm speed conditions, is first added TEA and is entered Row emulsification, neutralize 25min, add boric acid continue emulsify 15min, be evaporated under reduced pressure desolventizing, obtain solid content be 35% it is siliceous Boracic aqueous polyurethane, the mol ratio of the TEA and DMPA are 1:1, boron element in boric acid with amino-terminated siloxanes Element silicon mol ratio be 3:1；
3) the siliceous boracic aqueous polyurethane that appropriate step 2 is prepared is weighed, is poured into mould, then first in room temperature Under the conditions of stand to surface glued membrane dry, place into baking oven and dry 1h under conditions of 130 DEG C, obtain sample 3, it is to be measured.
Embodiment 4：The performance detection of siliceous boracic aqueous polyurethane
The sample 1-3 that embodiment 1-3 is prepared carries out the detection of hydrophobic, fire-retardant, suppression cigarette and mechanical property respectively, And sample 1-3 testing result with it is respective be not introduced into silicon, the performance of Water-based polyurethane elastomer control sample of boron is opposed Than, specific examination criteria and testing result are seen below shown in table 1-4, wherein, sample described in table 1-4 with water The increase percentage of contact angle, the decline percentage of maximum HRR, the decline percentage tensile strength of maximum smoke density Increase percentage and the increase percentage of elongation at break refer respectively to corresponding detection parameters phase with corresponding control sample Decline or increase percentage than for.Here so-called corresponding control sample is that is, such as sample 1, with Its corresponding control sample is equally to use mean molecule quantity not draw for what 1000 polyethylene glycol adipate glycol was prepared Enter the Water-based polyurethane elastomer of silicon, boron, same reason, for sample 2, its corresponding control sample uses to be same The aqueous polyurethane elastic for being not introduced into silicon, boron that the PTMG dihydric alcohol that mean molecule quantity is 2000 is prepared Body, sample 3 are as the same.From the data in table 1-4 this it appears that：Compared with being not introduced into the Water-based polyurethane elastomer of silicon, boron, The increase by more than 40.6% of the contact angle of sample and water can be made using siliceous boracic aqueous polyurethane disclosed by the invention, sample Maximum HRR declines more than 39.7%, maximum smoke density and declines more than 36.8%, tensile strength increase by more than 7.4%, Elongation at break increase by more than 9.7%.Data above analysis shows, existed using siliceous boracic aqueous polyurethane disclosed by the invention In actual application, the hydrophobic, fire-retardant of material, suppression cigarette and mechanical property can be effectively improved.
The hydrophobic performance test of the sample of table 1
The fire resistance test of the sample of table 2
The smoke suppressing test of the sample of table 3
The Mechanics Performance Testing of the sample of table 4

Claims (7)

  1. A kind of 1. siliceous boracic aqueous polyurethane, it is characterised in that：The chemical structural formula of the aqueous polyurethane is as follows：
    Wherein-R- structure is：-CH2CH2CH2-、-CH2CH2NHCH2CH2CH2- or-CH2CH2NHCH2CH2NHCH2CH2CH2-；
    -R1- structure be：
    -R2- structure be：
    N in structural formula is the arbitrary integer more than zero, and m is the integer between 1~30.
  2. 2. a kind of preparation method of siliceous boracic aqueous polyurethane as claimed in claim 1, comprises the following steps：
    A, by 1：2.2~3.0 mol ratio weighs macromolecule dihydric alcohol and mixed with TDI, in N270~90 DEG C are warming up under protection, 1~3h is reacted, DMPA is then first added and reacts 1~2h, add BDO and react 1~3h, be cooled to 60~70 DEG C, be then added dropwise Amino-terminated 0.5~1.5h of siloxane reactions, is cooled to 30~50 DEG C, obtains the polyurethane of siloxane blocking, in course of reaction Be added dropwise acetone regulation system viscosity, described DMPA, BDO, amino-terminated siloxanes and TDI mol ratio for 0.2~ 0.4:0.1~0.5:0.03~0.23:1, described macromolecule dihydric alcohol is polyester diol or polyether Glycols, described third The quality addition of ketone is the 50-150% of macromolecule dihydric alcohol quality；
    B, the polyurethane of siloxane blocking is placed under 1500~2000rpm speed conditions, first add TEA emulsified, in With 20~30min, add boric acid and continue 10~20min of emulsification, be evaporated under reduced pressure, obtain the siliceous boracic that solid content is 25~35% Aqueous polyurethane, the mol ratio of the TEA and DMPA are 0.8~1:1, boron element in boric acid with amino-terminated siloxanes Element silicon mol ratio be 2~3:1.
  3. 3. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, it is characterised in that：Ammonia in the step a The siloxanes of base end-blocking is 3- aminopropyl triethoxysilanes, N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes or diethyl The aminocarbonyl propyl trimethoxy silane of alkene three.
  4. 4. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, it is characterised in that：The step a is by 1: 2.6 mol ratio weighs macromolecule dihydric alcohol and mixed with TDI, in N280 DEG C are warming up under protection, 2h is reacted, then first adds DMPA reacts 1.5h, adds BDO reaction 2h, is cooled to 65 DEG C, and amino-terminated siloxanes is then added dropwise and continues to react 1h, drop Temperature obtains the polyurethane of siloxane blocking, the DMPA, BDO, amino-terminated siloxanes and TDI mol ratio are to 40 DEG C 0.28:0.23:0.21:1。
  5. 5. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, it is characterised in that：Acetone in the step a Quality addition be macromolecule dihydric alcohol quality 100%~150%.
  6. 6. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, it is characterised in that：The TEA's and DMPA Mol ratio is 0.9:1.
  7. 7. the preparation method of the siliceous boracic aqueous polyurethane according to right 2, it is characterised in that：Boron member in the boric acid The mol ratio of the plain element silicon with amino-terminated siloxanes is 2:1.
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