CN104263309A - Polyurethane adhesive and preparation method thereof - Google Patents
Polyurethane adhesive and preparation method thereof Download PDFInfo
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- CN104263309A CN104263309A CN201410477832.2A CN201410477832A CN104263309A CN 104263309 A CN104263309 A CN 104263309A CN 201410477832 A CN201410477832 A CN 201410477832A CN 104263309 A CN104263309 A CN 104263309A
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Abstract
The application provides a polyurethane adhesive and a preparation method thereof. The polyurethane adhesive contains 1-5% by weight of silylated nano-silicon dioxide modifier and has moderate viscosity and short curing time at room temperature, an adhesive layer is long in water boiling-resistant time and high in adhesive strength after complete curing, and the problems of low adhesive strength and poor water boiling resistance of an existing adhesive against hardwood and solid wood, in particular to redwood are solved.
Description
Technical field
The application relates to Wood Adhesive, is specifically related to a kind of polyurethane adhesive.
Background technology
Along with improving constantly of socio-economic development and living standards of the people, constantly increase the demand of timber and woodwork, the demand of corresponding Wood Adhesive is also significantly increased.The tackiness agent that current wood processing field uses mainly aldehyde adhesive stick comprises urea-formaldehyde resin (UF) glue, resol (PF) glue, melamine formaldehyde resin (MF) glue, and white glue with vinyl aqueous polyvinyl acetate emulsion (PVAc) glue etc.But, because aldehyde adhesive stick contains free formaldehyde, emitting formaldehyde gas contamination environment during applying glue, to be detrimental to health, during solidification glue-line shrinking percentage greatly easily come unglued, water-fast loss of properties on aging, cause its use to be restricted; Although white glue with vinyl has safety and environmental protection and the advantage such as to economize on resources, the aspect poor-performings such as its glued membrane frost resistance, water-fast thermotolerance and film formation at low temp, bonding strength is low, limits it and promotes and use.
This application discloses a kind of polyurethane adhesive, be polymerized by polyvalent alcohol and polyisocyanates, and use surface through the Nano-meter SiO_2 of silylation modification
2carry out modification.Improve the cohesive strength of tackiness agent, high temperature resistant poach performance, tackiness agent can be met in the service requirements of wood industry to high temperature resistant poach performance, high-adhesive-strength, have a extensive future.
Summary of the invention
According to an aspect of the application, be to provide a kind of silanization nano-material modified moisture curing polyurethane adhesive, this tackiness agent has high cohesive strength, excellent high temperature resistance poach performance and adhesiveproperties, the bonding timber of some special difficulty can be met, as hardwood and redwood, to high adhesion can and the service requirements of high temperature resistant poach performance.
The feature of described polyurethane adhesive is, nano-silicon dioxide modified dose of the silanization containing 1wt% ~ 5wt%.
Preferably, nano-silicon dioxide modified dose of described silanization, carries out surface silanization modification by the compd A with chemical structural formula shown in formula (I) to nano silicon and obtains:
Wherein, R
1, R
2, R
3independently be selected from the alkyl that carbonatoms is 1 ~ 20; Any positive integer of n optionally between 1 ~ 10.Further preferably, R described in formula (I)
1, R
2, R
3independently be selected from the alkyl that carbonatoms is 1 ~ 10; Any positive integer of n optionally between 1 ~ 5.Further preferably, the compd A with chemical structural formula shown in formula (I) is γ-aminopropyl triethoxysilane.
Described nano silicon is the silicon-dioxide of particle diameter 2 ~ 200nm.Preferably, described nano silicon is the silicon-dioxide of particle diameter 2 ~ 100nm.Further preferably, described nano silicon is the silicon-dioxide of particle diameter 5 ~ 20nm.
Preferably, nano-silicon dioxide modified dose of described silanization, prepared by following method: by nano silicon and compd A according to nano silicon: the weight ratio of compd A=10 ~ 15:1 ~ 3 is mixed in organic solvent, ultrasonicly under the condition of 50 DEG C be no less than 30min being no more than, through separation, washing, drying, obtain described silanization nano silicon.
Further preferably, nano-silicon dioxide modified dose of described silanization, is prepared by following method: by the Nano-meter SiO_2 of 10 ~ 15 weight parts
2be scattered in N-Methyl pyrrolidone solvent, at room temperature after ultrasonic disperse 1 ~ 2h, be heated to 35 ~ 45 DEG C, the γ-aminopropyl triethoxysilane of 1 ~ 3 weight part is added in reaction system, after stirring reaction 4 ~ 6h, carry out cooling, centrifugation, carry out repetitive scrubbing with dehydrated alcohol, after vacuum-drying, obtain the modified Nano SiO of surface silanization nanometer
2.
The introducing of silanization nano silicon can make urethane form certain cross-linked structure, simultaneously, silanization nano silicon plays the effect of physical crosslinking point as reinforcing filler in polymeric system, serves synergy to the adhesiveproperties such as cohesive strength, high temperature resistant poach performance improving tackiness agent.
According to another aspect of the application, provide a kind of preparation method of described polyurethane adhesive, it is characterized in that, at least containing following steps:
A) by through the polyvalent alcohol of vacuum hydro-extraction and polyisocyanates hybrid reaction, presoma I is obtained;
B) in the presoma I of step a) gained, add chainextender, obtain presoma II;
C) to step b) add nano-silicon dioxide modified dose of silanization in the presoma II of gained after, add solvent, obtain presoma III;
D) to step c) add catalyzer in the presoma III of gained, after mixing, obtain described polyurethane adhesive.
Preferably, step a) described in polyvalent alcohol be selected from oligomeric diols one or more; The molecular weight of described oligomeric diols is 500 ~ 3000.Further preferably, step a) described in polyvalent alcohol be polyoxypropyleneglycol.Further preferably, the molecular weight of described polyoxypropyleneglycol is 1000.
Preferably, step a) described in polyisocyanates be selected from vulcabond one or more.Further preferably, step a) described in polyisocyanates be ditan-4,4 '-vulcabond.
Preferably, step b) described in chainextender be selected from dibasic alcohol one or more.Further preferably, step b) described in chainextender be ethylene glycol.
Preferably, step c) described in solvent be selected from organic solvent one or more.Further preferably, step c) described in solvent be acetone.
Preferably, step c) described in nano-silicon dioxide modified dose of silanization, prepared by following method: by nano silicon and compd A according to nano silicon: the weight ratio of compd A=10 ~ 15:1 ~ 3 is mixed in organic solvent, ultrasonicly under the condition of 50 DEG C be no less than 30min being no more than, through separation, washing, drying, obtain nano-silicon dioxide modified dose of described silanization.
Preferably, step c) described in nano-silicon dioxide modified dose of silanization, by γ-aminopropyl triethoxysilane, finishing is carried out to nano silicon and obtains.Further preferably, described silanization nano silicon, is prepared by following method: by the Nano-meter SiO_2 of 10 ~ 15 weight parts
2be scattered in N-Methyl pyrrolidone solvent, at room temperature after ultrasonic disperse 1 ~ 2h, be heated to 35 ~ 45 DEG C, the γ-aminopropyl triethoxysilane of 1 ~ 3 weight part is added in reaction system, after stirring reaction 4 ~ 6h, carry out cooling, centrifugation, carry out repetitive scrubbing with dehydrated alcohol, after vacuum-drying, obtain nano-silicon dioxide modified dose of silanization.Further preferably, nano-silicon dioxide modified dose of described silanization, is prepared by following method: by the Nano-meter SiO_2 of 10 ~ 13 weight parts
2be scattered in the N-Methyl pyrrolidone solvent of 12 ~ 114 weight parts, at room temperature after ultrasonic disperse 1 ~ 2h, be heated to 35 ~ 45 DEG C, the γ-aminopropyl triethoxysilane of 2 ~ 3 weight parts is added in reaction system, after stirring reaction 4 ~ 6h, carry out cooling, centrifugation, carry out repetitive scrubbing with dehydrated alcohol, after vacuum-drying, obtain nano-silicon dioxide modified dose of silanization.
Preferably, steps d) described catalyzer is selected from containing one or more in the compound of alicyclic heterocyclic.Further preferably, steps d) described in catalyzer be 2,2 '-dimorpholine ethyl ether.
As one preferred embodiment, the preparation method of described polyurethane adhesive, is characterized in that, at least containing following steps:
The polyisocyanates of the polyvalent alcohol of the vacuum hydro-extraction of 95 ~ 115 weight parts with 65 ~ 85 weight parts a) mixes by step, and reaction is no less than 1 hour, obtains presoma I; Preferably, the range limit of the polyvalent alcohol add-on weight part of described vacuum hydro-extraction is optionally from 110,105, and lower limit is optionally from 95,100; The range limit of described polyisocyanates add-on weight part is optionally from 85,80, and lower limit is optionally from 70,75;
Step b) in presoma I, add the chainextender of 3.5 ~ 7 weight parts, reaction is no less than 1 hour, obtains presoma II; Preferably, the range limit of the weight part of described chainextender add-on is optionally from 7,6.5, and lower limit is optionally from 3.5,5;
Step c) in presoma II, add nano-silicon dioxide modified dose of the silanization of 5 ~ 12 weight parts, after reaction is no less than 1 hour, add the solvent of 40 ~ 60 weight parts, reaction is no less than 30min, obtains presoma III;
Steps d) in presoma III, add the catalyzer of 0.1 ~ 0.5 weight part, after mixing, reaction is no less than 10min, obtains described polyurethane adhesive.
Preferably, described step a), described step b) and described step c) all carry out being no more than at the temperature of 100 DEG C; Described steps d) carry out being no more than at the temperature of 50 DEG C.
Further preferably, described step is a) for reacting 1 ~ 3 hour at temperature of reaction 80 ~ 90 DEG C; Described step b) and step c) to be at temperature of reaction 80 ~ 90 DEG C reaction 2 ~ 4 hours; Described steps d) for reacting 20 ~ 40 minutes at temperature of reaction 35 ~ 40 DEG C.
As a preferably embodiment, the preparation method of described polyurethane adhesive, it is characterized in that, it is soft section with the polyoxypropyleneglycol of 95 ~ 115 weight parts, the ditan-4 of 65 ~ 85 weight parts, 4 '-vulcabond is hard section, the ethylene glycol of 3.5 ~ 7 weight parts is chainextender, the surface silanization nano silicon of 5 ~ 10 weight parts is properties-correcting agent, the acetone of 40 ~ 60 weight parts is solvent, 2 of 0.1 ~ 0.5 weight part, 2 '-dimorpholine ethyl ether is catalyzer, the nano-material modified moisture curing polyurethane adhesive of silanization is prepared by silanization is nano-silicon dioxide modified.
Described vacuum hydro-extraction polyoxypropyleneglycol is that polyoxypropyleneglycol is heated with stirring to 110 ~ 120 DEG C, and being evacuated to vacuum tightness is 0.08 ~ 0.1MPa, after vacuum hydro-extraction 1 ~ 2h to bubble-free effusion, passes into nitrogen and is cooled to 60 ~ 70 DEG C and obtains.
According to the another aspect of the application, there are provided a kind of wood binder, it is characterized in that, containing the polyurethane adhesive that aforementioned arbitrary polyurethane adhesive and/or aforementioned either method prepare.
The application provide the beneficial effect of technical scheme as follows:
(1) adopt γ-aminopropyl triethoxysilane to Nano-meter SiO_2
2carry out surface silanization nano modification, make modified Nano-meter SiO_2
2the organic degree of particle increases, and improve the consistency between urethane, meanwhile, silanization nano-silicon dioxide particle surface grafting contains end-NH
2organic molecule chain, can to react with the end-NCO base on polyurethane molecular chain, thus with the form of chemical bond by Nano-meter SiO_2
2be incorporated in polyurethane molecular chain, strengthen Nano-meter SiO_2 further
2with the consistency of urethane.
(2) silanization nano-silica surface is grafted with the-NH of more than three
2base, urethane can be made to form certain cross-linked structure, meanwhile, silanization nano silicon plays the effect of physical crosslinking point as reinforcing filler in polymeric system, serves synergy to the adhesiveproperties such as cohesive strength, high temperature resistant poach performance improving tackiness agent.
(3) this tackiness agent is monocomponent adhesive, does not need external reinforcement agent during use, easy to operate, brings great convenience to applying glue, is applicable to splicing and the processing of timber, is easy to promotion and application.
(4) the nano-material modified moisture curing polyurethane adhesive of silanization prepared of the application, its Adhensive performance is suitable with external similar Wood Adhesive performance, and external wood can be replaced to stick with glue the use of agent product.
Embodiment
For better understanding the application, below in conjunction with example, the application is described in detail further.The scope that this application claims protection is not limited to the scope that embodiment represents.
In embodiment, the particle diameter of nano silicon used is 5 ~ 20nm, purchased from Zhoushan Of Zhejiang Province nano material tomorrow company limited.
In embodiment, solid content adopts GB/T 2793-1995 " mensuration of tackiness agent non-volatile content ".
In embodiment, rotary viscosity measures on NDJ-1 rotational viscosimeter; Shearing resistance is in omnipotent mechanical test aircraft measurements.
In embodiment, the come unglued method of rate of JAS boiling water Soak Test is: 1, by test specimen health 7 days; 2, test specimen is put into boiling water to soak 4 hours; 3, the cold water put into by test specimen under room temperature soaks 1 hour; 4, test specimen is put into the baking oven at least 18 hours of 70 DEG C, level before being down to test to test specimen water ratio; 5, observe tree lace cracking situation, calculate tree lace and to come unglued rate, crack continuous length is greater than can counting of 3mm.The rate of coming unglued of test specimen calculates by formula (II):
K=L/ (2 × (a+b)) × 100% formula (II)
In formula:
K---rate of coming unglued, unit is percentage (%);
L---test specimen tree lace cracking length, unit is millimeter (mm)
A---test specimen glueds joint the length of part, and unit is millimeter (mm)
B---test specimen glueds joint the width of part, and unit is millimeter (mm).
The preparation of comparative example 0#
The polyoxypropyleneglycol of 100g is heated with stirring to 118 DEG C, and being evacuated to vacuum tightness is 0.1MPa, after vacuum hydro-extraction 2h to bubble-free effusion, passes into nitrogen and is cooled to 70 DEG C and obtains vacuum hydro-extraction polyoxypropyleneglycol.80g ditan-4 is added in vacuum hydro-extraction polyoxypropyleneglycol, 4 '-vulcabond, reacts 2h at being warming up to 85 DEG C, adds 6.5g ethylene glycol and carries out chain extension, the acetone adding 50g after reaction 3h dilutes, be cooled to 40 DEG C after reaction 0.5h, add 2 of 0.1g, 2 '-dimorpholine ethyl ether violent stirring 20min, room temperature discharging is down to after stirring, airtight preservation in drying receptacle, the unmodified sample of gained, is designated as sample 0
#.
Embodiment 1 sample 1
#preparation
(1) 10g Nano-meter SiO_2 is got
2mix with 12g solvent N-methyl pyrilidone, at room temperature after ultrasonic disperse 1h, be heated to 35 DEG C, 3g γ-aminopropyl triethoxysilane is added in reaction system, after reaction 5h, carry out cooling, centrifugation, carry out repetitive scrubbing with dehydrated alcohol, after vacuum-drying, obtain silanization nano silicon.
(2) polyoxypropyleneglycol of 100g is heated with stirring to 115 DEG C, being evacuated to vacuum tightness is 0.1MPa, after vacuum hydro-extraction 1.5h to bubble-free effusion, passes into nitrogen and is cooled to 65 DEG C and obtains vacuum hydro-extraction polyoxypropyleneglycol.
(3) by 80g ditan-4, 4 '-vulcabond adds in step (2) gained vacuum hydro-extraction polyoxypropyleneglycol, 2h is reacted at being warming up to 85 DEG C, add 6.5g ethylene glycol and carry out chain extension, reaction 3h obtains base polyurethane prepolymer for use as, step (1) the gained silanization nano silicon adding 10g again carries out modification, the acetone adding 50g after reaction 3h dilutes, 40 DEG C are cooled to after reaction 0.5h, add 2 of 0.1g, 2 '-dimorpholine ethyl ether violent stirring 30min, room temperature discharging is down to after stirring, airtight preservation in drying receptacle, namely the nano-material modified moisture curing polyurethane adhesive of silanization is obtained, be designated as sample 1#.
The preparation of embodiment 2 sample 2#
(1) 13g Nano-meter SiO_2 is got
2mix with 15g solvent N-methyl pyrilidone, at room temperature after ultrasonic disperse 1h, be heated to 35 DEG C, 2g γ-aminopropyl triethoxysilane is added in reaction system, after reaction 4h, carry out cooling, centrifugation, carry out repetitive scrubbing with dehydrated alcohol, after vacuum-drying, obtain silanization nano silicon.
(2) polyoxypropyleneglycol of 110g is heated with stirring to 110 DEG C, being evacuated to vacuum tightness is 0.08MPa, after vacuum hydro-extraction 1h to bubble-free effusion, passes into nitrogen and is cooled to 60 DEG C and obtains vacuum hydro-extraction polyoxypropyleneglycol.
(3) by 70g ditan-4, 4 '-vulcabond adds in step (2) gained vacuum hydro-extraction polyoxypropyleneglycol, 2h is reacted at being warming up to 80 DEG C, add 5g ethylene glycol to carry out chain extending reaction 2h and obtain base polyurethane prepolymer for use as, the silanization nano silicon adding 8.5g step (1) gained again carries out modification, the acetone adding 60g after reaction 3h dilutes, 35 DEG C are cooled to after reaction 0.5h, add 2 of 0.3g, 2 '-dimorpholine ethyl ether violent stirring 20min, room temperature discharging is down to after stirring, airtight preservation in drying receptacle, namely the nano-material modified moisture curing polyurethane adhesive of silanization is obtained, be designated as sample 2#.
Embodiment 3 sample 3
#preparation
(1) 11g Nano-meter SiO_2 is got
2mix with 114g solvent N-methyl pyrilidone, at room temperature after ultrasonic disperse 1.5h, be heated to 35 DEG C, 2g γ-aminopropyl triethoxysilane is added in reaction system, after reaction 4.5h, carry out cooling, centrifugation, carry out repetitive scrubbing with dehydrated alcohol, after vacuum-drying, obtain silanization nano silicon;
(2) polyoxypropyleneglycol of 95g is heated with stirring to 120 DEG C, being evacuated to vacuum tightness is 0.1MPa, after vacuum hydro-extraction 2h to bubble-free effusion, passes into nitrogen and is cooled to 70 DEG C and obtains vacuum hydro-extraction polyoxypropyleneglycol.
(3) by 85g ditan-4, 4 '-vulcabond joins in step (2) gained vacuum hydro-extraction polyoxypropyleneglycol, 3h is reacted at being warming up to 85 DEG C, add 7g ethylene glycol to carry out chain extending reaction 3.5h and obtain base polyurethane prepolymer for use as, the silanization nano silicon adding 5g step (1) gained again carries out modification, the acetone adding 40g after reaction 3h dilutes, 38 DEG C are cooled to after reaction 0.5h, add 2 of 0.5g, 2 '-dimorpholine ethyl ether violent stirring 30min, room temperature discharging is down to after stirring, airtight preservation in drying receptacle, namely the nano-material modified moisture curing polyurethane adhesive of silanization is obtained, be designated as sample 3#.
Embodiment 4 sample 4
#preparation
(1) 12g Nano-meter SiO_2 is got
2mix with 16g solvent N-methyl pyrilidone, at room temperature after ultrasonic disperse 2h, be heated to 35 DEG C, 2.5g γ-aminopropyl triethoxysilane is added in reaction system, after reaction 4h, carry out cooling, centrifugation, carry out repetitive scrubbing with dehydrated alcohol, after vacuum-drying, obtain silanization nano silicon;
(2) polyoxypropyleneglycol of 105g is heated with stirring to 115 DEG C, being evacuated to vacuum tightness is 0.09MPa, after vacuum hydro-extraction 1.5h to bubble-free effusion, passes into nitrogen and is cooled to 65 DEG C and obtains vacuum hydro-extraction polyoxypropyleneglycol.
(3) by 75g ditan-4, in 4 '-vulcabond step (2) gained vacuum hydro-extraction polyoxypropyleneglycol, 2h is reacted at being warming up to 90 DEG C, add 3.5g ethylene glycol to carry out chain extending reaction 4h and obtain base polyurethane prepolymer for use as, the silanization nano silicon adding 12g step (1) gained again carries out modification, the acetone adding 55g after reaction 2.5h dilutes, 35 DEG C are cooled to after reaction 0.5h, add 2 of 0.2g, 2 '-dimorpholine ethyl ether violent stirring 40min, room temperature discharging is down to after stirring, airtight preservation in drying receptacle, namely the nano-material modified moisture curing polyurethane adhesive of silanization is obtained, be designated as sample 4#.
Embodiment 5 sample 0
#~ sample 4
#performance test
To sample 0
#~ sample 4
#measure, Specifeca tion speeification is as shown in table 1.
Table 1
As can be seen from data in table 1, the sample 1 that method prepares according to the application
#~ sample 4
#, the sample 0 prepared with the comparative example not adopting silanization nano-silicon dioxide modified
#compare, under room temperature condition, viscosity is suitable for, without the need to external reinforcement agent during use, and constructability.Set time is short, after solidification, bonding strength can destroy material completely, can resistance to 100 DEG C of high temperature poach for up to more than 6h, can meet timber especially after the solidification of redwood bonding or board material splice to the bonding demand of high-adhesive-strength and high temperature resistant poach performance, be easy to promotion and application.
Embodiment 6 sample 5
#with sample 6
#preparation and property is tested
According to the synthesis condition in embodiment 1 and raw material dosage, only by 13g Nano-meter SiO_2 in step (1)
2change 15g Nano-meter SiO_2 into
2, 2g γ-aminopropyl triethoxysilane changes 1g γ-aminopropyl triethoxysilane into, other preparation conditions and step constant, the nano-material modified moisture curing polyurethane adhesive of gained silanization, is designated as sample 5
#.
According to the synthesis condition in embodiment 1 and raw material dosage, only change the polyoxypropyleneglycol of 100g in step (3) polyoxypropyleneglycol of 115g into, 80g ditan-4,4 '-vulcabond changes 65g ditan-4 into, 4 '-vulcabond, step (1) the gained silanization nano silicon of 10g changes step (1) the gained silanization nano silicon of 5g into, other preparation conditions and step constant, the nano-material modified moisture curing polyurethane adhesive of gained silanization, is designated as sample 6
#.
To sample 5
#with sample 6
#measure, its Specifeca tion speeification is all the same with the performance perameter of sample 1# ~ 4# in table 1.
Although the application with preferred embodiment openly as above; but be not for limiting claim; any those skilled in the art are under the prerequisite not departing from the application's design; can make some possible variations and amendment, the scope that therefore protection domain of the application should define with the application's claim is as the criterion.
Claims (10)
1. a polyurethane adhesive, is characterized in that, nano-silicon dioxide modified dose of the silanization containing 1wt% ~ 5wt%.
2. polyurethane adhesive according to claim 1, is characterized in that, nano-silicon dioxide modified dose of described silanization, carries out surface silanization modification obtain by the compd A with chemical structural formula shown in formula (I) to nano silicon:
Wherein, R
1, R
2, R
3independently be selected from the alkyl that carbonatoms is 1 ~ 20; Any positive integer of n optionally between 1 ~ 10.
3. polyurethane adhesive according to claim 2, it is characterized in that, nano-silicon dioxide modified dose of described silanization, prepared by following method: by nano silicon and compd A according to nano silicon: the weight ratio of compd A=10 ~ 15:1 ~ 3 is mixed in organic solvent, ultrasonicly under the condition of 50 DEG C be no less than 30min being no more than, through separation, washing, drying, obtain described silanization nano silicon.
4. prepare a method for polyurethane adhesive described in claim 1, it is characterized in that, at least containing following steps:
A) by through the polyvalent alcohol of vacuum hydro-extraction and polyisocyanates hybrid reaction, presoma I is obtained;
B) in the presoma I of step a) gained, add chainextender, obtain presoma II;
C) to step b) add nano-silicon dioxide modified dose of silanization in the presoma II of gained after, add solvent, obtain presoma III;
D) to step c) add catalyzer in the presoma III of gained, after mixing, obtain described polyurethane adhesive.
5. method according to claim 4, is characterized in that, step a) described in polyvalent alcohol be selected from oligomeric diols one or more; Step a) described in polyisocyanates be selected from vulcabond one or more; Step b) described in chainextender be selected from dibasic alcohol one or more; Step c) described in solvent be selected from organic solvent one or more; Steps d) described catalyzer is selected from containing one or more in the compound of alicyclic heterocyclic.
6. method according to claim 4, is characterized in that, step a) described in polyvalent alcohol be polyoxypropyleneglycol; Step a) described in polyisocyanates be ditan-4,4 '-vulcabond; Step b) described in chainextender be ethylene glycol; Step c) described in solvent be acetone; Steps d) described in catalyzer be 2,2 '-dimorpholine ethyl ether.
7. method according to claim 4, is characterized in that, step c) described in nano-silicon dioxide modified dose of silanization, by γ-aminopropyl triethoxysilane, finishing is carried out to nano silicon and obtains.
8. method according to claim 4, is characterized in that, step is a) mixed by the polyisocyanates of the polyvalent alcohol of the vacuum hydro-extraction of 95 ~ 115 weight parts with 65 ~ 85 weight parts, and reaction is no less than 1 hour, obtains presoma I; Step b) for adding the chainextender of 3.5 ~ 7 weight parts in presoma I, reaction is no less than 1 hour, obtains presoma II; Step c) for adding nano-silicon dioxide modified dose of the silanization of 5 ~ 12 weight parts in presoma II, after reaction is no less than 1 hour, add the solvent of 40 ~ 60 weight parts, reaction is no less than 30min, obtains presoma III; Steps d) for adding the catalyzer of 0.1 ~ 0.5 weight part in presoma III, after mixing, reaction is no less than 10min, obtains described polyurethane adhesive.
9. method according to claim 4, is characterized in that, described step a), described step b) and described step c) all carry out being no more than at the temperature of 100 DEG C; Described steps d) carry out being no more than at the temperature of 50 DEG C.
10. a wood binder, is characterized in that, containing the polyurethane adhesive that method described in polyurethane adhesive described in any one of claim 1-3 and/or any one of claim 4-9 prepares.
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| CN105860913A (en) * | 2016-04-18 | 2016-08-17 | 深圳清华大学研究院 | Binding agent for supercapacitor, electrode plate of supercapacitor and preparation method of electrode plate of supercapacitor |
| CN107488433A (en) * | 2017-08-22 | 2017-12-19 | 安徽艾米伦特建材科技有限公司 | Modified polyurethane binding agent and preparation method thereof |
| CN109749692A (en) * | 2017-11-07 | 2019-05-14 | 中国科学院福建物质结构研究所 | A kind of heat resistant type wet-solidifying single-component polyurethane adhesive and its preparation method and application |
| CN109627410A (en) * | 2018-12-21 | 2019-04-16 | 山东诺威聚氨酯股份有限公司 | High-adhesion puffed rice sole polyurethane binder and preparation method thereof |
| CN111662573A (en) * | 2020-06-20 | 2020-09-15 | 万华化学集团股份有限公司 | Vegetable oil and organic silicon composite modified UV-curable nano silicon dioxide, preparation method and application thereof |
| CN111662573B (en) * | 2020-06-20 | 2021-10-22 | 万华化学集团股份有限公司 | Vegetable oil and organic silicon composite modified UV-curable nano silicon dioxide, preparation method and application thereof |
| CN114437361A (en) * | 2021-12-24 | 2022-05-06 | 中国科学院福建物质结构研究所 | Inorganic-organic hybrid material, preparation method thereof and application of modified polyurethane prepared from inorganic-organic hybrid material as adhesive |
| CN114437361B (en) * | 2021-12-24 | 2022-12-06 | 中国科学院福建物质结构研究所 | Inorganic-organic hybrid material, preparation method thereof and application of modified polyurethane prepared from inorganic-organic hybrid material as adhesive |
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