CN107698732A - A kind of preparation method of 3 d function polyurethane material - Google Patents
A kind of preparation method of 3 d function polyurethane material Download PDFInfo
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Abstract
The invention belongs to polyurethane material technical field, and in particular to a kind of preparation method of 3 d function polyurethane material, including：Cyclohexane diisocyanate and PEO glycol are added into reactor, ultrasonic mixing forms mixed reaction solution；Polycaprolactone glycol and metallocene catalyst are slowly added dropwise into mixed reaction solution simultaneously, while the 4h of microwave reaction 2, obtain base polyurethane prepolymer for use as；Sodium alginate and dispersant are added into absolute ethyl alcohol, the 20min of ultrasonic reaction 10, obtain scattered complexing agent；Initiator and foaming agent are added in base polyurethane prepolymer for use as, scattered complexing agent and organic calcium is slowly added to, seals the 4h of temperature-pressure 2, obtain functional polyurethane precast body；Functional polyurethane precast body is put into the progress 4h of ultrasonic reaction 2 in reactor, sealing pressing stands 10 15min of reaction, 3 d function polyurethane material is obtained after pressure release cooling.The present invention solves the problems, such as that current physical solidification is ineffective, forms physical chemistry combination curing, improves the performance of polyurethane.
Description
Technical field
The invention belongs to polyurethane material technical field, and in particular to a kind of preparation side of 3 d function polyurethane material
Method.
Background technology
Polyurethane is taught and its worked together by Germanization scholar Otto Bayer and synthesized first in nineteen thirty-seven, also known as poly-
Carbamate, refer to the big of carbamate groups (- NHCOO-) in strand or urea groups (- NHCOONH-) repeated arrangement
Molecule.Polyurethane applications are extensive, excellent performance, can synthesize the totally different polyurethane products of performance using different monomers.From
Molecular structure sees that polyurethane is typically the block polymer being made up of soft segment and hard section, and the polyalcohol such as polyethers or polyester constitutes
The soft segment of polyurethane, containing C -- C single bond and C-O singly-bounds in soft segment, the internal rotation frequency of singly-bound is very high, and does not stop, so
At normal temperatures, soft segment conformation is more, very submissive as a mixed and disorderly unordered ball of string in random coil shape, while soft segment is poly-
Proportion is larger in urethane, imparts polyurethane fabulous cryogenic property and elasticity.Isocyanates and life after chain extender reaction
Into carbamate groups etc. constitute the hard section of polyurethane.Contain highly polar carbamate groups or aromatic radical in hard section
Group so that the active force between segment is big.Hard section imparts the excellent mechanical property of polyurethane, such as hardness, tensile strength.By
Thermodynamically there is incompatibility in hard section and soft segment, be easily clumped together to form microcell between hard section segment, microcell point
It is distributed in soft segment, forms a kind of discontinuous island structure, this phenomenon is called microphase-separated, and the structure spy of polyurethane
Sign.
Because the heat resistance, water resistance and weatherability of polyurethane are poor, its application is have impact on, therefore it is changed
Property to expand application, by effort for many years, it was discovered by researchers that blending, physical modification and chemical modification can be passed through
Method improves the performance of polyurethane.Physical modification is typically to add inorganic nano material or some in polyurethane to have special work(
The filler of energy, assign polyurethane certain performance, be prepared into the polyurethane material of function admirable.Physical modification is typically in polyurethane
Middle addition inorganic nano material or some there is the filler of specific function, assign polyurethane certain performance, be prepared into function admirable
Polyurethane material.By introducing the group of good thermal stability in polyurethane molecular chain, heat resistance of polyurethane etc. is improved,
Chemical modification is the more method of modifying of research.
Inorganic nano material is mainly put into polyurethane by physical modification at present, and valence link is not formed with polyurethane, therefore
The solidification effect of inorganic nano material is poor, it is easy to is influenceed by polyurethane, the problems such as causing to come off.
The content of the invention
For the problems of the prior art, the present invention provides
To realize above technical purpose, the technical scheme is that：A kind of preparation of 3 d function polyurethane material
Method, it is characterised in that its step is as follows：
Step 1, cyclohexane diisocyanate and PEO glycol are added into reactor, ultrasonic mixing forms mixed
Close reaction solution；
Step 2, polycaprolactone glycol and metallocene catalyst are slowly added dropwise into mixed reaction solution simultaneously, while microwave
2-4h is reacted, obtains base polyurethane prepolymer for use as；
Step 3, sodium alginate and dispersant are added into absolute ethyl alcohol, ultrasonic reaction 10-20min, obtains scattered network
Mixture
Step 4, initiator and foaming agent are added in base polyurethane prepolymer for use as, stirred, be slowly added to scattered complexing agent
With organic calcium, temperature-pressure 2-4h is sealed, obtains functional polyurethane precast body；
Step 5, functional polyurethane precast body is put into progress ultrasonic reaction 2-4h in reactor, sealing pressing stands anti-
10-15min is answered, 3 d function polyurethane material is obtained after pressure release cooling.
The mass ratio of cyclohexane diisocyanate and PEO glycol in the step 1 is 10-15:3, it is described super
The supersonic frequency of sound mixing is 2.5-5.5kHz, and ultrasonic temperature is 40-60 DEG C, and the ultrasonic mixing time is 20-40min.
The addition of polycaprolactone glycol in the step 2 is the 30-50% of cyclohexane diisocyanate quality, described
The addition of metallocene catalyst is the 5-15% of cyclohexane diisocyanate quality, and the metallocene catalyst is using two cyclopentadienyls
Iron.
The rate of addition of polycaprolactone glycol in the step 2 is 3-7mL/min, the dropwise addition of the metallocene catalyst
Speed is 2-4g/min, and the power of the microwave reaction is 100-250W, and temperature is 90-120 DEG C, mixing speed 1200-
2500r/min。
The concentration of sodium alginate in the step 3 is 5-8g/L, and the dispersant concentration is 1-3g/L, the dispersant
Using ethylene-acrylic acid copolymer or ethylene-vinyl acetate copolymer.
The frequency of ultrasonic reaction in the step 3 is 4.5-7.5kHz, and temperature is 50-70 DEG C.
Initiator addition in the step 4 is the 10-15% of cyclohexane diisocyanate quality, foaming agent addition
It is that cyclohexane diisocyanate quality is 5-9%, the mixing speed of the stirring is 4000-5000r/min, and the initiator is adopted
With ammonium persulfate, the foaming agent uses ammonium carbonate.
The addition of scattered complexing agent in the step 4 is the 20-25% of cyclohexane diisocyanate quality, described to have
The addition of machine calcium is the 18-24% of cyclohexane diisocyanate quality., the addition speed of the scattered complexing agent and organic calcium
For 5-10g/min, the organic calcium uses calcium lactate or calcium gluconate.
The pressure of sealing temperature-pressure reaction in the step 4 is 10-15MPa, and temperature is 120-150 DEG C.
The frequency of ultrasonic reaction in the step 5 is 10-20kHz, and temperature is 100-120 DEG C, and the sealing pressing is quiet
The temperature for putting reaction is 80-90 DEG C, pressure 8-12MP.
Cyclohexane diisocyanate and PEO glycol are carried out ultrasonic mixing by step 1, by ultrasound by hexamethylene
Diisocyanate and PEO glycol are opened, and are formed good scattered, reach mixed effect, low-frequency ultrasound can rise
To good dispersion effect, without causing reaction between the two.
Polycaprolactone glycol is slowly added to mixed reaction solution by step 2, under the conditions of microwave reaction with the isocyanic acid of hexamethylene two
Ester and PEO glycol are reacted to form polyurethane precast body, and good catalysis effect can be played by adding metallocene catalyst
Fruit, catalytic activity can be further improved under microwave action；The mode being slowly added to can ensure that the crosslinking between three is anti-
Should, while the effect for being slowly added to play control reaction of metallocene catalyst, with the reduction of reaction material, catalyst
Increase can ensure its stable catalytic reaction.
Step 3 adds sodium alginate and dispersant into absolute ethyl alcohol, ultrasound can be utilized to be dispersed to nothing
Water-ethanol, reaches the complexing alcohol liquid of dispersion, solves the problems, such as the dispersed bad of sodium alginate by dispersant.
Initiator and foaming agent are put into polyurethane precast body by step 4, after stirring, form good dispersion
System, initiator and foaming agent are infiltrated into inside precast body, form good mixed effect；Scattered complexing agent is slowly added to having
Machine calcium, reacted under the conditions of sealing pressing heating, disperse complexing agent and organic calcium is subjected to crosslinking reaction, while in foaming agent
Under being acted on initiator, polyurethane precast body forms substantial amounts of bubble cavity, and it is pre- that calcium complex is connected to polyurethane by initiator
On body processed, good and firm valence link connection is formed, reaches modified effect, while the bridging property that precast body is formed in itself is three-dimensional
Structure, calcium complex can be solidified in bubble hole, form physics and fix, obtain functional polyurethane precast body.
Functional polyurethane precast body is carried out ultrasonic reaction by step 5, can open the bad valence link of connection effect, simultaneously
Intermolecular vigor can be increased, polyurethane is tightened up；The mode that sealing pressing is stood can form pressure in outer surface, ensure poly-
Urethane outer surface and internal pressure differential, play squeezing action, ensure the steadiness of three-dimensional structure, obtain the poly- ammonia of 3 d functionization
Ester material.
From the above, it can be seen that the present invention possesses advantages below：
1. the mechanical performance of 3 d function polyurethane material provided by the invention is improved with hot property, solve
The problem of physical solidification is ineffective at present, physics-chemical combined solidification is formed, improve the performance of polyurethane.
2. preparation method provided by the invention is simple and easy, controlling is strong, suitable for industrialization.
3. polyurethane prepared by the present invention has good hydrophily, and hydrophily Modulatory character is strong.
Embodiment
Describe the present invention in detail in conjunction with the embodiments, but any restriction is not done to the claim of the present invention.
Embodiment 1
A kind of preparation method of 3 d function polyurethane material, it is characterised in that its step is as follows：
Step 1, cyclohexane diisocyanate and PEO glycol are added into reactor, ultrasonic mixing forms mixed
Close reaction solution；
Step 2, polycaprolactone glycol and metallocene catalyst are slowly added dropwise into mixed reaction solution simultaneously, while microwave
2h is reacted, obtains base polyurethane prepolymer for use as；
Step 3, sodium alginate and dispersant are added into absolute ethyl alcohol, ultrasonic reaction 10min, obtains scattered complexing agent
Step 4, initiator and foaming agent are added in base polyurethane prepolymer for use as, stirred, be slowly added to scattered complexing agent
With organic calcium, temperature-pressure 2h is sealed, obtains functional polyurethane precast body；
Step 5, functional polyurethane precast body is put into progress ultrasonic reaction 2h in reactor, sealing pressing stands reaction
10min, 3 d function polyurethane material is obtained after pressure release cooling.
The mass ratio of cyclohexane diisocyanate and PEO glycol in the step 1 is 10:3, the ultrasound
The supersonic frequency of mixing is 2.5kHz, and ultrasonic temperature is 40 DEG C, and the ultrasonic mixing time is 20min.
The addition of polycaprolactone glycol in the step 2 is the 30% of cyclohexane diisocyanate quality, the cyclopentadienyl
The addition of metallic catalyst is the 5% of cyclohexane diisocyanate quality, and the metallocene catalyst uses ferrocene.
The rate of addition of polycaprolactone glycol in the step 2 is 3mL/min, and the dropwise addition of the metallocene catalyst is fast
Spend for 2g/min, the power of the microwave reaction is 100W, and temperature is 90 DEG C, mixing speed 1200r/min.
The concentration of sodium alginate in the step 3 is 5g/L, and the dispersant concentration is 1g/L, and the dispersant uses
Ethylene-acrylic acid copolymer.
The frequency of ultrasonic reaction in the step 3 is 4.5kHz, and temperature is 50 DEG C.
Initiator addition in the step 4 is the 10% of cyclohexane diisocyanate quality, and foaming agent addition is
Cyclohexane diisocyanate quality is 5%, and the mixing speed of the stirring is 4000r/min, and the initiator uses persulfuric acid
Ammonium, the foaming agent use ammonium carbonate.
The addition of scattered complexing agent in the step 4 is the 20% of cyclohexane diisocyanate quality, described organic
The addition of calcium is the 18% of cyclohexane diisocyanate quality., the addition speed of the scattered complexing agent and organic calcium is 5g/
Min, the organic calcium use calcium lactate.
The pressure of sealing temperature-pressure reaction in the step 4 is 10MPa, and temperature is 120 DEG C.
The frequency of ultrasonic reaction in the step 5 is 10kHz, and temperature is 100 DEG C, and the sealing pressing stands reaction
Temperature is 80 DEG C, pressure 8MP.
Embodiment 2
A kind of preparation method of 3 d function polyurethane material, it is characterised in that its step is as follows：
Step 1, cyclohexane diisocyanate and PEO glycol are added into reactor, ultrasonic mixing forms mixed
Close reaction solution；
Step 2, polycaprolactone glycol and metallocene catalyst are slowly added dropwise into mixed reaction solution simultaneously, while microwave
4h is reacted, obtains base polyurethane prepolymer for use as；
Step 3, sodium alginate and dispersant are added into absolute ethyl alcohol, ultrasonic reaction 20min, obtains scattered complexing agent
Step 4, initiator and foaming agent are added in base polyurethane prepolymer for use as, stirred, be slowly added to scattered complexing agent
With organic calcium, temperature-pressure 4h is sealed, obtains functional polyurethane precast body；
Step 5, functional polyurethane precast body is put into progress ultrasonic reaction 4h in reactor, sealing pressing stands reaction
15min, 3 d function polyurethane material is obtained after pressure release cooling.
The mass ratio of cyclohexane diisocyanate and PEO glycol in the step 1 is 15:3, the ultrasound
The supersonic frequency of mixing is 5.5kHz, and ultrasonic temperature is 60 DEG C, and the ultrasonic mixing time is 40min.
The addition of polycaprolactone glycol in the step 2 is the 50% of cyclohexane diisocyanate quality, the cyclopentadienyl
The addition of metallic catalyst is the 15% of cyclohexane diisocyanate quality, and the metallocene catalyst uses ferrocene.
The rate of addition of polycaprolactone glycol in the step 2 is 7mL/min, and the dropwise addition of the metallocene catalyst is fast
Spend for 4g/min, the power of the microwave reaction is 250W, and temperature is 120 DEG C, mixing speed 2500r/min.
The concentration of sodium alginate in the step 3 is 8g/L, and the dispersant concentration is 3g/L, and the dispersant uses
Ethylene-vinyl acetate copolymer.
The frequency of ultrasonic reaction in the step 3 is 7.5kHz, and temperature is 70 DEG C.
Initiator addition in the step 4 is the 15% of cyclohexane diisocyanate quality, and foaming agent addition is
Cyclohexane diisocyanate quality is 9%, and the mixing speed of the stirring is 5000r/min, and the initiator uses persulfuric acid
Ammonium, the foaming agent use ammonium carbonate.
The addition of scattered complexing agent in the step 4 is the 25% of cyclohexane diisocyanate quality, described organic
The addition of calcium is the 24% of cyclohexane diisocyanate quality., the addition speed of the scattered complexing agent and organic calcium is
10g/min, the organic calcium use calcium gluconate.
The pressure of sealing temperature-pressure reaction in the step 4 is 15MPa, and temperature is 150 DEG C.
The frequency of ultrasonic reaction in the step 5 is 20kHz, and temperature is 120 DEG C, and the sealing pressing stands reaction
Temperature is 90 DEG C, pressure 12MP.
Embodiment 3
A kind of preparation method of 3 d function polyurethane material, it is characterised in that its step is as follows：
Step 1, cyclohexane diisocyanate and PEO glycol are added into reactor, ultrasonic mixing forms mixed
Close reaction solution；
Step 2, polycaprolactone glycol and metallocene catalyst are slowly added dropwise into mixed reaction solution simultaneously, while microwave
3h is reacted, obtains base polyurethane prepolymer for use as；
Step 3, sodium alginate and dispersant are added into absolute ethyl alcohol, ultrasonic reaction 15min, obtains scattered complexing agent
Step 4, initiator and foaming agent are added in base polyurethane prepolymer for use as, stirred, be slowly added to scattered complexing agent
With organic calcium, temperature-pressure 3h is sealed, obtains functional polyurethane precast body；
Step 5, functional polyurethane precast body is put into progress ultrasonic reaction 3h in reactor, sealing pressing stands reaction
4min, 3 d function polyurethane material is obtained after pressure release cooling.
The mass ratio of cyclohexane diisocyanate and PEO glycol in the step 1 is 13:3, the ultrasound
The supersonic frequency of mixing is 4kHz, and ultrasonic temperature is 50 DEG C, and the ultrasonic mixing time is 30min.
The addition of polycaprolactone glycol in the step 2 is the 40% of cyclohexane diisocyanate quality, the cyclopentadienyl
The addition of metallic catalyst is the 10% of cyclohexane diisocyanate quality, and the metallocene catalyst uses ferrocene.
The rate of addition of polycaprolactone glycol in the step 2 is 5mL/min, and the dropwise addition of the metallocene catalyst is fast
Spend for 3g/min, the power of the microwave reaction is 150W, and temperature is 110 DEG C, mixing speed 1800r/min.
The concentration of sodium alginate in the step 3 is 7g/L, and the dispersant concentration is 2g/L, and the dispersant uses
Ethylene-acrylic acid copolymer.
The frequency of ultrasonic reaction in the step 3 is 6kHz, and temperature is 60 DEG C.
Initiator addition in the step 4 is the 13% of cyclohexane diisocyanate quality, and foaming agent addition is
Cyclohexane diisocyanate quality is 7%, and the mixing speed of the stirring is 4500r/min, and the initiator uses persulfuric acid
Ammonium, the foaming agent use ammonium carbonate.
The addition of scattered complexing agent in the step 4 is the 23% of cyclohexane diisocyanate quality, described organic
The addition of calcium is the 21% of cyclohexane diisocyanate quality., the addition speed of the scattered complexing agent and organic calcium is 8g/
Min, the organic calcium use calcium lactate.
The pressure of sealing temperature-pressure reaction in the step 4 is 13MPa, and temperature is 140 DEG C.
The frequency of ultrasonic reaction in the step 5 is 15kHz, and temperature is 110 DEG C, and the sealing pressing stands reaction
Temperature is 85 DEG C, pressure 10MP.
Performance test
In summary, the present invention has advantages below：
1. the mechanical performance of 3 d function polyurethane material provided by the invention is improved with hot property, solve
The problem of physical solidification is ineffective at present, physics-chemical combined solidification is formed, improve the performance of polyurethane.
2. preparation method provided by the invention is simple and easy, controlling is strong, suitable for industrialization.
3. polyurethane prepared by the present invention has good hydrophily, and hydrophily Modulatory character is strong.
It is understood that above with respect to the specific descriptions of the present invention, it is merely to illustrate the present invention and is not limited to this
Technical scheme described by inventive embodiments.It will be understood by those within the art that still the present invention can be carried out
Modification or equivalent substitution, to reach identical technique effect；As long as meet use needs, all protection scope of the present invention it
It is interior.
Claims (10)
1. a kind of preparation method of 3 d function polyurethane material, it is characterised in that its step is as follows：
Step 1, cyclohexane diisocyanate and PEO glycol are added into reactor, it is anti-that ultrasonic mixing forms mixing
Answer liquid；
Step 2, polycaprolactone glycol and metallocene catalyst are slowly added dropwise into mixed reaction solution simultaneously, while microwave reaction
2-4h, obtain base polyurethane prepolymer for use as；
Step 3, sodium alginate and dispersant are added into absolute ethyl alcohol, ultrasonic reaction 10-20min, obtains scattered complexing agent
Step 4, initiator and foaming agent are added in base polyurethane prepolymer for use as, stirred, be slowly added to scattered complexing agent with having
Machine calcium, temperature-pressure 2-4h is sealed, obtains functional polyurethane precast body；
Step 5, functional polyurethane precast body is put into progress ultrasonic reaction 2-4h in reactor, sealing pressing stands reaction
10-15min, 3 d function polyurethane material is obtained after pressure release cooling.
A kind of 2. preparation method of 3 d function polyurethane material according to claim 1, it is characterised in that：The step
The mass ratio of cyclohexane diisocyanate and PEO glycol in rapid 1 is 10-15:3, the supersonic frequency of the ultrasonic mixing
Rate is 2.5-5.5kHz, and ultrasonic temperature is 40-60 DEG C, and the ultrasonic mixing time is 20-40min.
A kind of 3. preparation method of 3 d function polyurethane material according to claim 1, it is characterised in that：The step
The addition of polycaprolactone glycol in rapid 2 is the 30-50% of cyclohexane diisocyanate quality, the metallocene catalyst
Addition is the 5-15% of cyclohexane diisocyanate quality, and the metallocene catalyst uses ferrocene.
A kind of 4. preparation method of 3 d function polyurethane material according to claim 1, it is characterised in that：The step
The rate of addition of polycaprolactone glycol in rapid 2 is 3-7mL/min, and the rate of addition of the metallocene catalyst is 2-4g/
Min, the power of the microwave reaction is 100-250W, and temperature is 90-120 DEG C, mixing speed 1200-2500r/min.
A kind of 5. preparation method of 3 d function polyurethane material according to claim 1, it is characterised in that：The step
The concentration of sodium alginate in rapid 3 is 5-8g/L, and the dispersant concentration is 1-3g/L, and the dispersant uses ethylene-propylene
Acid copolymer or ethylene-vinyl acetate copolymer.
A kind of 6. preparation method of 3 d function polyurethane material according to claim 1, it is characterised in that：The step
The frequency of ultrasonic reaction in rapid 3 is 4.5-7.5kHz, and temperature is 50-70 DEG C.
A kind of 7. preparation method of 3 d function polyurethane material according to claim 1, it is characterised in that：The step
Initiator addition in rapid 4 is the 10-15% of cyclohexane diisocyanate quality, and foaming agent addition is the isocyanide of hexamethylene two
Acid esters quality is 5-9%, and the mixing speed of the stirring is 4000-5000r/min, and the initiator uses ammonium persulfate, described
Foaming agent uses ammonium carbonate.
A kind of 8. preparation method of 3 d function polyurethane material according to claim 1, it is characterised in that：The step
The addition of scattered complexing agent in rapid 4 is the 20-25% of cyclohexane diisocyanate quality, and the addition of the organic calcium is
The 18-24% of cyclohexane diisocyanate quality., the addition speed of the scattered complexing agent and organic calcium is 5-10g/min, institute
State organic calcium and use calcium lactate or calcium gluconate.
A kind of 9. preparation method of 3 d function polyurethane material according to claim 1, it is characterised in that：The step
The pressure of sealing temperature-pressure reaction in rapid 4 is 10-15MPa, and temperature is 120-150 DEG C.
A kind of 10. preparation method of 3 d function polyurethane material according to claim 1, it is characterised in that：It is described
The frequency of ultrasonic reaction in step 5 is 10-20kHz, and temperature is 100-120 DEG C, and the sealing pressing stands the temperature of reaction
For 80-90 DEG C, pressure 8-12MP.
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