A kind of sub-micron SiO2The preparation of/poly ethyldiol modified polyurathamc composite
Method
Technical field
The invention belongs to technical field of polymer composite materials, is related to sub-micron SiO2The poly- ammonia of/poly ethyldiol modified foaming
The preparation method of ester composite.
Background technology
Polyethylene glycol and SiO2What system was formed is a kind of non-Newtonian fluid material with characteristic shear thickening effect
(STF).Under the conditions of quick washing, the viscosity of STF materials can improve the 2-3 order of magnitude, can be in some milliseconds from mobility
Preferable liquid umklappen is the solid-state that viscosity is high, intensity is higher, therefore its shock resistance is excellent, and physics-change
It is stable to learn property.Microporous foam polyurethane material is then a kind of excellent buffering energy-absorbing material, is widely used in physical culture protection and uses
The fields such as product, buffering shoe-pad, vibration protection.Such as STF and microporous foam polyurethane material are organically combined, then are expected to obtain one
The advanced composite material (ACM) that kind impact resistance is increased dramatically.In addition, in actual applications, due to the solidification of polyethylene glycol
Point is minimum only to -15 DEG C (ethylene glycol), and after silica is added, its freezing point is more more than 0 DEG C, therefore is applied to
Temperature range causes certain limitation.How STF to be combined with microporous foam polyurethane, and improves its anti-seismic design,
It is the key issue for needing to solve.
The content of the invention
The defects of to overcome present in prior art, the present invention provide a kind of poly ethyldiol modified foaming of sub-micron SiO2/
The preparation method of compound polyurethane material, can solve the problem that above-mentioned technical problem.
Technical scheme is used by the invention solves its technical problem:Design a kind of sub-micron SiO2/ polyethylene glycol
The preparation method of modified foaming compound polyurethane material, carry out successively as steps described below:
Step 1:Weigh certain mass than polyethylene glycol, sub-micron SiO2, be uniformly mixed at a certain temperature,
Then the end hydroxyl silicone oil for adding certain mass obtains STF base-materials;
Step 2:The STF base-materials described in step 1 are taken to be obtained after being well mixed with polyurathamc A material in polyurathamc
Component A, STF base-material and component A mass ratio reach certain value;
Step 3:The component A described in step 2 is taken to be mixed with polyurathamc B material, crosslinked foaming is at a certain temperature
It can obtain composite.
Preferably, the polyethylene glycol described in step 1 is ethylene glycol, polyethylene glycol 200, polyethylene glycol 400, poly- second two
Any one in alcohol 600 or polyethylene glycol-800.
Preferably, the end hydroxyl silicone oil degree of polymerization described in step 1 is from 80-1000.
Preferably, the polyethylene glycol described in step 1 and sub-micron SiO2Certain mass ratio is 55-60:45-40.
Preferably, the certain temperature described in step 1 is 80 DEG C.
Preferably, the particle diameter of submicron silicon dioxide described in step 1 is 100-950nm.
Preferably, end hydroxyl silicone oil described in step 1 and polyethylene glycol/SiO2Mass ratio be 1-30:99-70.
Preferably, the polyurathamc A material described in step 2 are polyhydric alcohol conjugate material.
Preferably, the mass ratio of the STF base-materials described in step 2 and component A is 0.5-18:99.5-82.
Preferably, the polyurathamc B material described in step 3 are isocyanates.
Preferably, the certain temperature described in step 3 is 70 DEG C.
Beneficial effect is possessed by the present invention:
1st, the present invention is compound by polyethylene glycol/SiO2 STF materials formed and blown polyurethane materials, and for preparing answers
Condensation material can pass through the fast of silica dioxide granule in material when being sheared or being impacted in the STF materials of dispersed phase distribution
Speed is reunited and absorbed and the part energy that dissipates, so as to realize the enhancing to foamed polyurethane matrix;After impact, non-destructive
Deformation can recover.The preparation technology is easy to operate, suitable for merchandized handling.
2nd, polyurathamc is made up of two-component in the present invention, and component A is polyhydric alcohol conjugate, and B component is isocyanates
(MDI).A kind of this polyurathamc has the advantages that foam cells uniform and smooth, physical and chemical stability is good.The present invention plans
Polyurathamc and the shear thickening liquid (STF) that polyethylene glycol/sub-micron SiO2 is formed are compound, on the one hand utilize STF materials
Shear thickening effect, make composite when being impacted, absorbed and dissipated by the shear thickening materials in dispersed phase distribution
Part energy;On the other hand, the addition of polyethylene glycol can be improved the percent opening of polyurethane foam;And matrix material
Polyurathamc plays its resilience, and composite restPoses under elastic reaction after non-demolition impact.The present invention
The polyurathamc that obtained polyethylene glycol/SiO2 is modified has more excellent anti-impact compared with unmodified polyurathamc
Hit performance and barrier propterty.
Embodiment
Comparative example
By polyurathamc A material and B material mixed foaming shapings, mixed proportion 100:55, prepare the foamed board of 1 cm thick
Material, obtain common blown polyurethane materials.
Embodiment one
A kind of preparation method of the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/, as steps described below
Carry out successively:
Step 1:It is well mixed using polyethylene glycol 200 with particle diameter 100nm silica, then adding the degree of polymerization is
STF base-materials, polyethylene glycol 200 is made in 80 end hydroxyl silicone oil:Silica quality ratio is 60:40, end hydroxyl silicone oil:Poly- second
Glycol/silica mixture mass ratio is 1:99.
Step 2:STF base-materials and polyurathamc A material are mixed to get foaming Tooth preparation, STF base-materials and polyurathamc
A constituent masses ratio is 0.5:99.5.
Step 3:By the foaming Tooth preparation that step 2 obtains, (mixed proportion is fixed as with polyurathamc B material mixed foaming
100:55) foaming plate of 1 cm thick is prepared, that is, obtains the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/.
Embodiment two
A kind of preparation method of the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/, as steps described below
Carry out successively:
Step 1:It is well mixed using polyethylene glycol 200 with particle diameter 950nm silica, then adding the degree of polymerization is
STF base-materials, polyethylene glycol 200 is made in 1000 end hydroxyl silicone oil:Silica quality ratio is 55:45, terminal hydroxy group silicon
Oil:Polyethylene glycol/silicon dioxide mixture quality ratio is 30:70.
Step 2:STF base-materials and polyurathamc A material are mixed to get foaming Tooth preparation, STF base-materials and polyurathamc
A constituent masses ratio is 18:82.
Step 3:The foaming Tooth preparation that step 2 obtains is prepared to the hair of 1 cm thick with polyurathamc B material mixed foamings
Sheet material is steeped, that is, obtains the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/.
Embodiment three
A kind of preparation method of the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/, as steps described below
Carry out successively:
Step 1:It is well mixed using polyethylene glycol 400 with particle diameter 100nm silica, then adding the degree of polymerization is
STF base-materials, polyethylene glycol 400 is made in 80 end hydroxyl silicone oil:Silica quality ratio is 60:40, end hydroxyl silicone oil:Poly- second
Glycol/silica mixture mass ratio is 1:99.
Step 2:STF base-materials and polyurathamc A material are mixed to get foaming Tooth preparation, STF base-materials and polyurathamc
A constituent masses ratio is 0.5:99.5.
Step 3:The foaming Tooth preparation that step 2 obtains is prepared to the hair of 1 cm thick with polyurathamc B material mixed foamings
Sheet material is steeped, that is, obtains the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/.
Example IV
A kind of preparation method of the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/, as steps described below
Carry out successively:
Step 1:It is well mixed using polyethylene glycol 400 with particle diameter 950nm silica, the rear degree of polymerization that adds is
STF base-materials, polyethylene glycol 400 is made in 1000 end hydroxyl silicone oil:Silica quality ratio is 55:45, terminal hydroxy group silicon
Oil:Polyethylene glycol/silicon dioxide mixture quality ratio is 30:70.
Step 2:STF base-materials and polyurathamc A material are mixed to get foaming Tooth preparation, STF base-materials and polyurathamc
A constituent masses ratio is 18:82.
Step 3:The foaming Tooth preparation that step 2 obtains is prepared to the hair of 1 cm thick with polyurathamc B material mixed foamings
Sheet material is steeped, that is, obtains the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/.
Embodiment five
A kind of preparation method of the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/, as steps described below
Carry out successively:
Step 1:It is well mixed using Macrogol 600 with particle diameter 100nm silica, then adding the degree of polymerization is
STF base-materials, Macrogol 600 is made in 80 end hydroxyl silicone oil:Silica quality ratio is 60:40, end hydroxyl silicone oil:Poly- second
Glycol/silica mixture mass ratio is 1:99.
Step 2:STF base-materials and polyurathamc A material are mixed to get foaming Tooth preparation, STF base-materials and polyurathamc
A constituent masses ratio is 0.5:99.5.
Step 3:The foaming Tooth preparation that step 2 obtains is prepared to the hair of 1 cm thick with polyurathamc B material mixed foamings
Sheet material is steeped, that is, obtains sub-micron SiO2/ poly ethyldiol modified polyurathamc composite.
Embodiment six
A kind of preparation method of the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/, as steps described below
Carry out successively:
Step 1:It is well mixed using Macrogol 600 with particle diameter 950nm silica, the rear degree of polymerization that adds is
STF base-materials, Macrogol 600 is made in 1000 end hydroxyl silicone oil:Silica quality ratio is 55:45, terminal hydroxy group silicon
Oil:Polyethylene glycol/silicon dioxide mixture quality ratio is 30:70.
Step 2:STF base-materials and polyurathamc A material are mixed to get foaming Tooth preparation, STF base-materials and polyurathamc
A constituent masses ratio is 18:82.
Step 3:The foaming Tooth preparation that step 2 obtains is prepared to the hair of 1 cm thick with polyurathamc B material mixed foamings
Sheet material is steeped, that is, obtains the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/.
Embodiment seven
A kind of preparation method of the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/, as steps described below
Carry out successively:
Step 1:It is well mixed using ethylene glycol with particle diameter 100nm silica, then adds the end that the degree of polymerization is 80
STF base-materials, ethylene glycol is made in hydroxy silicon oil:Silica quality ratio is 60:40, end hydroxyl silicone oil:Ethylene glycol/silica
Mixture quality ratio is 1:99.
Step 2:STF base-materials and polyurathamc A material are mixed to get foaming Tooth preparation, STF base-materials and polyurathamc
A constituent masses ratio is 0.5:99.5.
Step 3:The foaming Tooth preparation that step 2 obtains is prepared to the hair of 1 cm thick with polyurathamc B material mixed foamings
Sheet material is steeped, that is, obtains the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/.
Embodiment eight
A kind of preparation method of the glycol-modified polyurathamc composites of sub-micron SiO2/, as steps described below according to
Secondary progress:
Step 1:It is well mixed using ethylene glycol with particle diameter 950nm silica, it is rear to add the end that the degree of polymerization is 1000
STF base-materials, ethylene glycol is made in hydroxy silicon oil:Silica quality ratio is 55:45, end hydroxyl silicone oil:Polyethylene glycol/bis-
Aktivton mass ratio is 30:70.
Step 2:STF base-materials and polyurathamc A material are mixed to get foaming Tooth preparation, STF base-materials and polyurathamc
A constituent masses ratio is 1:99.
Step 3:The foaming Tooth preparation that step 2 obtains is prepared to the hair of 1 cm thick with polyurathamc B material mixed foamings
Sheet material is steeped, that is, obtains the poly ethyldiol modified polyurathamc composites of sub-micron SiO2/.
Each sample obtained above is tested according to EN14120 standards, and its test result is as follows:
As can be seen here, the blown polyurethane materials being modified using method provided by the invention, its barrier propterty are substantially better than
Common blown polyurethane materials.
It should be noted last that:Above example is only to illustrative and not limiting technical scheme, although ginseng
The present invention is described in detail according to above-described embodiment, it will be apparent to an ordinarily skilled person in the art that:Still can be to this
Invention is modified or equivalent substitution, and any modification or partial replacement without departing from the spirit and scope of the present invention, its is equal
It should cover among scope of the presently claimed invention.