CN110194828A - A kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover - Google Patents
A kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover, the pure and mild MDI type performed polymer of polymer polyol, reaction generates the polyurethane elastomer matrix with high-intensitive toughness；The micro-pore elastomer structure with excellent energy-absorbing, damping effect is formed simultaneously by using chemical blowing mode the density for generating polyurethane elastomer is effectively reduced；Solid-liquid phase change, liquid-gas phase transformation, and the high solid phase change material particle containing multiple crystallizations water of latent heat of phase change can occur when by adulterating a certain amount of effect by blast impulse wave energy in the feed, to further increase the energy-absorbing effect of the elastomer.It by required raw material, after mixing uniformly, is poured into the outer protective cover mold of special anti-explosion tank, arrives the light polyurethane elastomer anti-explosion tank outer protective cover with preferable energy-absorbing effect after foamed curing molding demoulding.The safety of explosion-proof equipment can effectively be enhanced, while significantly mitigating the weight of explosion-proof equipment.
Description
Technical field
The invention belongs to explosion-proof lamp fields, and in particular to a kind of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover
Preparation.
Background technique
The explosion-proof principle of the anti-explosion tank appliances of traditional public place is: using compared with thick steel plate, cooperating certain high intensity
Multi-layer compound structure shell is made in flexible polymer material, come the diffusion of the fragment and energy that prevent explosion from generating, plays reduction
Brisance, the effect for preventing the harm of explosion wave and fragment generation.Since major part is highdensity metal material, this
Body weight it is very big (tradition can anti-500gTNT equivalent explosive charge anti-explosion tank, single weight is more than 300 kilograms), and with preventing
The increase of quick-fried equivalent, the size and thickness of traditional anti-explosion tank will be further increased, and weight also further increases, basic by manpower
On can not achieve and fast move, need professional mobile with professed machine traction device.In addition the use of traditional anti-explosion tank is also
It is required that the anti-explosion tank for being loaded with explosive is transferred to open field, and require top that there must be 6 meters or more spaces, and avoid
There may be the article that splash is hurted sb.'s feelings after the damage such as spandrel girder, glass, pendent lamp, use condition is extremely harsh.Traditional anti-explosion tank
High weight and harsh use condition, cause its it is practical use very time-consuming, this is public for what time is life
For safety anti-explosive, application value is had a greatly reduced quality.
Therefore, developing can significantly absorb, weaken shock wave energy that explosion generates and density is low, stability is good
New material for cause explosion-proof for public safety, have very heavy for preparing public place anti-explosion tank appliances
The meaning wanted.
Have using tetrahydrofuran polyether or polycaprolactone polyethers and MDI as microcellular polyurethane elastomer prepared by raw material excellent
Resilience, tensile strength still with higher and fracture elongation when compared with low-density, by being introduced in the base containing multiple
The high latent heat of phase change phase transformation powder stuffing of the crystallization water, is remarkably improved the energy-absorbing effect of the micro-pore elastomer, can effectively inhale
Consumption blast impulse wave energy is received, weakens the destructive power of explosion wave, suitable for preparing public place security protection
Light polyurethane elastomer anti-explosion tank outer protective cover of new generation.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of system of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover
Preparation Method.
The purpose of the present invention is what is be achieved through the following technical solutions.
A kind of high tenacity low-density polyurethane elastomer of energy-absorbing material containing phase transformation of the invention is passed through by component A and B component
Foaming in container is injected into after mixed at high speed to be prepared；
Component A is polyether polyol combination material, including following component: it is steady to expand even agent, chemical foaming agent, foam for polyether polyol
Determine agent, catalyst, mill base, phase transformation powder powder stuffing；
It is 100 parts of calculating, the mass content of other each components with the quality of polyether polyol are as follows:
40-55 parts of polyether polyol
2-8 parts of chain extender
0.1-0.4 parts of chemical foaming agent
0.2-2 parts of foam stabiliser
0.2-2 parts of catalyst
0.5-5 parts of mill base
5-40 parts of phase transformation powder stuffing
Component A is obtained after the above component is mixed in proportion.
B component is after methyl diphenylene diisocyanate (MDI) reacts 4-6h at 80-90 DEG C with polyether polyol, to add
Enter 0.01% polymerization inhibitor to get to Storage period length using-NCO as the prepolymer of end-capping group.
A kind of high tenacity low-density polyurethane method for producing elastomers of energy-absorbing material containing phase transformation of the invention, step
Are as follows:
(1) polyether polyol is pressed with chain extender, chemical foaming agent, foam stabiliser, catalyst, solid first powder stuffing
According to quality than uniformly mixing after precise, component A is obtained；
(2) after methyl diphenylene diisocyanate being reacted 4-6h at 80-90 DEG C with polyether polyol, 0.01% resistance is added
Poly- agent is to get to Storage period length using-NCO as the prepolymer B component of end-capping group；
(3) component A and B component are not preheating to 40 ~ 50 DEG C, then according to mass ratio 1:1 precise, are injected after mixed at high speed
In the characteristics of being sprayed with polyurethane release agent to surface anti-explosion tank outer protective cover mold.Mold will heat in advance, and temperature is at 60 ~ 70 DEG C
Between.Then mold is put into heating 10-20 minutes in 60 ~ 80 DEG C of convection ovens, then demoulding carries out surface repairing to get arriving
The high tenacity low-density polyurethane elastomer anti-explosion tank outer protective cover of the energy-absorbing material containing phase transformation.
In above-mentioned steps (1), polyether polyol can are as follows: degree of functionality 2, the polytetrahydrofuran that molecular weight is 1000 or 2000
Polyalcohol (PTMG)；Degree of functionality is 2, the polycaprolactone polyol (PCL) that molecular weight is 1000 or 2000；Degree of functionality is 2, molecule
The polycarbonate polyol (PCD) that amount is 1000 or 2000；Degree of functionality is 3, the polyoxypropylene polyol that molecular weight is 5000
(EP330) one or more；It is preferred that degree of functionality is 2, the polytetrahydrofuran polyol and function that molecular weight is 1000 or 2000
Degree is 3, the polyoxypropylene polyol (EP330) that molecular weight is 5000；
In above-mentioned steps (1), expand even agent are as follows: the small molecule compound containing 2 hydroxyls or amino, such as ethylene glycol, propylene glycol, 1,
4- butanediol, 1.6- hexylene glycol, diglycol, dipropylene glycol, the chloro- 4,4' diaminodiphenylmethane of 3,3'- bis-, two
The one or more of ethyltoluene diamines, 3,5- disulfide group toluenediamine etc., preferably 1,4-butanediol；
In above-mentioned steps (1), chemical foaming agent are as follows: H2O；
In above-mentioned steps (1), foam stabiliser are as follows: optional for the organosilicone surfactants of high resilience polyurethane foam
The trade mark of Jiangsu Mei Side company is AK-7719, the foam stabiliser of AK-7730；It is preferred that AK-7730 foam stabiliser；
In above-mentioned steps (1), catalyst is that A33(contains the liquid catalyst of 33% triethylene diamine), bis- (the diformazan ammonia of BDMAE(
Base ethyl)) ether, T12One or more, preferably A33 and the T of (dibutyl tin dilaurate), stannous octoate12Mixed catalyst；
In above-mentioned steps (1), phase transformation powder powder stuffing are as follows: for phase transition temperature between 45 ~ 60 DEG C, latent heat of phase change is higher
Inorganic hydrate containing multiple crystallizations water, optionally has: Na2S2O3.5H2O (48 DEG C of phase transition temperature, latent heat of phase change 201J/g),
MgSO4.7H248.5 DEG C of O(phase transition temperature, latent heat of phase change 202J/g), Ni (NO3)2.6H257 DEG C of O(phase transition temperature, latent heat of phase change
169J/g), CH3COONa.3H258 DEG C of O(phase transition temperature, latent heat of phase change 267J/g), MgCl.4H258 DEG C of O(phase transition temperature, phase transformation
Latent heat 178J/g) one or more, preferably containing more than the crystallization water and MgSO4.7H that latent heat of phase change is high2O and Ni (NO3)2.6H2O is applied after crushed 400 meshes.
In above-mentioned steps (2), polyether polyol can are as follows: degree of functionality 2, the polytetrahydrofuran that molecular weight is 1000 or 2000
Polyalcohol (PTMG)；Degree of functionality is 2, the polycaprolactone polyol (PCL) that molecular weight is 1000 or 2000；Degree of functionality is 2, molecule
The polycarbonate polyol (PCD) that amount is 1000 or 2000；It is preferred that degree of functionality is 2, the poly- tetrahydro that molecular weight is 1000 or 2000
Furan polyols；
In above-mentioned steps (2), polymerization inhibitor are as follows: diethylene glycol bischloroformates；
Polyurethane release agent in above-mentioned steps (3) are as follows: solvent type silicon systems release agent；
Component A and B component in above-mentioned steps (3) need to be previously heated to 40 ~ 50 DEG C, and component A and B component use mass ratio
For 1:01.0 ± 0.1, molar ratio is 1:1.05 ± 0.05, and preferred mass ratio is 1:1.0 ± 0.02, the molar ratio of-NCO/-OH
For 1:1.04 ± 0.02.
Mold in above-mentioned steps (3) is preheating to 60 ~ 70 DEG C in advance, injects the polyurethane elastomer of the filler of energy-absorbing containing phase transformation
After raw material, mold is put into heating 10-20 minutes in 60 ~ 80 DEG C of convection ovens.
Beneficial effect
The invention discloses a kind of preparation methods of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover.This method by
The high latent heat of phase change phase transformation powder containing multiple crystallizations water is introduced in low-density and high-strength flexible polyurethane elastomer matrix to fill out
Material, by second-order phase transition process and gas expansion negative function, significantly improves the energy-absorbing effect of the micro-pore elastomer, effectively inhales
Receipts consume blast impulse wave energy, weaken the destructive power of explosion wave.The anti-explosion tank outer protective cover of this method preparation is used for
Public place security protection lightweight anti-explosion tank of new generation, can significantly mitigate the weight of existing anti-explosion tank, be the explosive personnel of a line
The novel ability of a kind of light portable, non-contact explosive removing is provided, joint disposal ability is improved.
Specific embodiment
Embodiment 1
A kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover, comprising the following steps:
(1) polytetrahydrofuran polyol for being 2000 by 2 degree of functionality molecular weight of 48 mass parts, 15 mass parts, 3 degree of functionality molecule
The polyoxypropylene polyol EP330 that amount is 5000, the H with the 1,4-butanediol of 3.5 mass parts, 0.25 mass parts2O, 1.0 matter
Measure the T of the AK-7730 of part, the A33,0.01 mass parts of 0.1 mass parts12, measure the catalyst of part, the MgSO4.7H of 15 mass parts2O
With the Ni (NO of 15 mass parts3)2.6H2O crosses the phase transformation powder stuffing of 400 meshes, more uniform than after precise according to quality
Mixing, obtains component A；
It (2) is 2000 by the methyl diphenylene diisocyanate (MDI) of 50 mass parts and 2 degree of functionality molecular weight of 50 mass parts
After reacting 4-6h at 80-90 DEG C, the diethylene glycol bischloroformates polymerization inhibitor of 0.01 mass parts is added in polytetrahydrofuran polyol
Agent is to get to Storage period length using-NCO as the prepolymer B component of end-capping group；
(3) component A and B component are not preheating to 40 ~ 50 DEG C, then according to mass ratio 1:1 precise, are injected after mixed at high speed
In the characteristics of being sprayed with polyurethane release agent to surface anti-explosion tank outer protective cover mold.Mold is previously heated to 60 ~ 70 DEG C.Then will
Mold is put into heating 10-20 minutes in 60 ~ 80 DEG C of convection ovens, and then demoulding carries out surface repairing to get energy-absorbing containing phase transformation is arrived
The high tenacity low-density polyurethane elastomer anti-explosion tank outer protective cover of material.
The performance test results of outer protective cover obtained are shown in Table 1.
Embodiment 2
A kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover, comprising the following steps:
(1) polycaprolactone polyol for being 2000 by 2 degree of functionality molecular weight of 48 mass parts, 15 mass parts, 3 degree of functionality molecular weight
H for 5000 polyoxypropylene polyol EP330, with the 1,4-butanediol of 3.5 mass parts, 0.25 mass parts2O, 1.0 mass
Part AK-7730,0.1 mass parts A33,0.01 mass parts T12, measure the catalyst of part, the MgSO4.7H of 15 mass parts2O and
Ni (the NO of 15 mass parts3)2.6H2O crosses the phase transformation powder stuffing of 400 meshes, according to quality than uniformly mixing after precise
It closes, obtains component A；
It (2) is 2000 by the methyl diphenylene diisocyanate (MDI) of 50 mass parts and 2 degree of functionality molecular weight of 50 mass parts
After reacting 4-6h at 80-90 DEG C, the diethylene glycol bischloroformates polymerization inhibitor of 0.01 mass parts is added in polycaprolactone polyol
Agent is to get to Storage period length using-NCO as the prepolymer B component of end-capping group；
(3) component A and B component are not preheating to 40 ~ 50 DEG C, then according to mass ratio 1:1 precise, are injected after mixed at high speed
In the characteristics of being sprayed with polyurethane release agent to surface anti-explosion tank outer protective cover mold.Mold is previously heated to 60 ~ 70 DEG C.Then will
Mold is put into heating 10-20 minutes in 60 ~ 80 DEG C of convection ovens, and then demoulding carries out surface repairing to get energy-absorbing containing phase transformation is arrived
The high tenacity low-density polyurethane elastomer anti-explosion tank outer protective cover of material.
The performance test results of outer protective cover obtained are shown in Table 1.
Embodiment 3
A kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover, comprising the following steps:
(1) polytetrahydrofuran polyol for being 2000 by 2 degree of functionality molecular weight of 40 mass parts, 2 degree of functionality molecules of 8 mass parts
The polytetrahydrofuran polyol that amount is 1000, the polyoxypropylene polyol that 15 mass parts, 3 degree of functionality molecular weight is 5000
EP330, and 3, the H of the 1,4-butanediol of 0 mass parts, 0.25 mass parts2O, the AK-7730 of 1.0 mass parts, 0.1 mass parts
The T of A33,0.01 mass parts12, measure the catalyst of part, the MgSO4.7H of 15 mass parts2Ni (the NO of O and 15 mass parts3)2.6H2O
The phase transformation powder stuffing for crossing 400 meshes obtains component A according to quality than uniformly mixing after precise；
It (2) is 2000 by the methyl diphenylene diisocyanate (MDI) of 50 mass parts and 2 degree of functionality molecular weight of 50 mass parts
After reacting 4-6h at 80-90 DEG C, the diethylene glycol bischloroformates polymerization inhibitor of 0.01 mass parts is added in polytetrahydrofuran polyol
Agent is to get to Storage period length using-NCO as the prepolymer B component of end-capping group；
(3) component A and B component are not preheating to 40 ~ 50 DEG C, then according to mass ratio 1:1 precise, are injected after mixed at high speed
In the characteristics of being sprayed with polyurethane release agent to surface anti-explosion tank outer protective cover mold.Mold is previously heated to 60 ~ 70 DEG C.Then will
Mold is put into heating 10-20 minutes in 60 ~ 80 DEG C of convection ovens, and then demoulding carries out surface repairing to get energy-absorbing containing phase transformation is arrived
The high tenacity low-density polyurethane elastomer anti-explosion tank outer protective cover of material.
The performance test results of outer protective cover obtained are shown in Table 1.
Embodiment 4
A kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover, comprising the following steps:
(1) polytetrahydrofuran polyol for being 2000 by 2 degree of functionality molecular weight of 48 mass parts, 15 mass parts, 3 degree of functionality molecule
The polyoxypropylene polyol EP330 that amount is 5000, and 3, the H of the 1,4-butanediol of 0 mass parts, 0.25 mass parts2O, 1.0 matter
Measure the T of the AK-7730 of part, the A33,0.01 mass parts of 0.1 mass parts12, measure the catalyst of part, the MgSO4.7H of 20 mass parts2O
With the Ni (NO of 10 mass parts3)2.6H2O crosses the phase transformation powder stuffing of 400 meshes, it is more uniform than after precise according to quality
Mixing, obtains component A；
It (2) is 2000 by the methyl diphenylene diisocyanate (MDI) of 50 mass parts and 2 degree of functionality molecular weight of 50 mass parts
After reacting 4-6h at 80-90 DEG C, the diethylene glycol bischloroformates polymerization inhibitor of 0.01 mass parts is added in polytetrahydrofuran polyol
Agent is to get to Storage period length using-NCO as the prepolymer B component of end-capping group；
(3) component A and B component are not preheating to 40 ~ 50 DEG C, then according to mass ratio 1:1 precise, are injected after mixed at high speed
In the characteristics of being sprayed with polyurethane release agent to surface anti-explosion tank outer protective cover mold.Mold is previously heated to 60 ~ 70 DEG C.Then will
Mold is put into heating 10-20 minutes in 60 ~ 80 DEG C of convection ovens, and then demoulding carries out surface repairing to get energy-absorbing containing phase transformation is arrived
The high tenacity low-density polyurethane elastomer anti-explosion tank outer protective cover of material.
The performance test results of outer protective cover obtained are shown in Table 1.
A kind of performance of the phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover of table 1
Claims (9)
1. a kind of preparation method of phase transformation energy-absorbing polyurethane elastomer anti-explosion tank outer protective cover, which is characterized in that step are as follows:
(1) polyether polyol is pressed with chain extender, chemical foaming agent, foam stabiliser, catalyst, phase transformation powder stuffing
According to quality than uniformly mixing after precise, component A is obtained；
(2) after methyl diphenylene diisocyanate being reacted 4-6h at 80-90 DEG C with polyether polyol, 0.01% resistance is added
Poly- agent is to get to Storage period length using-NCO as the prepolymer B component of end-capping group；
(3) component A and B component are not preheating to 40 ~ 50 DEG C, then according to mass ratio 1:1 precise, are injected after mixed at high speed
In the characteristics of being sprayed with polyurethane release agent to surface anti-explosion tank outer protective cover mold；Mold will heat in advance, and temperature is at 60 ~ 70 DEG C
Between；Then mold is put into 60 ~ 80 DEG C of convection ovens and is heated 10-20 minutes, demoulding carries out surface and repairs to get to containing phase
Become the high tenacity low-density polyurethane elastomer anti-explosion tank outer protective cover of energy-absorbing material.
2. preparation method according to claim 1, it is characterised in that: polyether polyol as described in step (1) can be official
Energy degree is 2, the polytetrahydrofuran polyol (PTMG) that molecular weight is 1000 or 2000；Degree of functionality is 2, molecular weight be 1000 or
2000 polycaprolactone polyol (PCL)；Degree of functionality is 2, the polycarbonate polyol (PCD) that molecular weight is 1000 or 2000；
Degree of functionality is 3, molecular weight be 5000 polyoxypropylene polyol (EP330) it is one or more.
3. preparation method according to claim 1, it is characterised in that: even agent is to contain 2 hydroxyls for expansion as described in step (1)
The small molecule compound of base or amino, such as ethylene glycol, propylene glycol, 1,4-butanediol, 1.6- hexylene glycol, diglycol, one
Contracting dipropylene glycol, the chloro- 4,4' diaminodiphenylmethane of 3,3'- bis-, diethyl toluene diamine, 3,5- disulfide group toluenediamine etc.
It is one or more of；The chemical foaming agent is H2O；The foam stabiliser are as follows: for having for high resilience polyurethane foam
Machine silicon class surfactant, the trade mark of optional Jiangsu Mei Side company are AK-7719, the foam stabiliser of AK-7730.
4. preparation method according to claim 1, it is characterised in that: catalyst as described in step (1) contains for A33(
The liquid catalyst of 33% triethylene diamine), BDMAE(bis- (dimethylaminoethyls)) ether, T12It is (dibutyl tin dilaurate), pungent
Sour stannous it is one or more.
5. preparation method according to claim 1, it is characterised in that: phase transformation powder powder as described in step (1)
Filler is phase transition temperature between 45 ~ 60 DEG C, and the higher inorganic hydrate containing multiple crystallizations water of latent heat of phase change optionally has:
Na2S2O3.5H2O (48 DEG C of phase transition temperature, latent heat of phase change 201J/g), MgSO4.7H248.5 DEG C of O(phase transition temperature, latent heat of phase change
202J/g), Ni (NO3)2.6H257 DEG C of O(phase transition temperature, latent heat of phase change 169J/g), CH3COONa.3H258 DEG C of O(phase transition temperature,
Latent heat of phase change 267J/g), MgCl.4H258 DEG C of O(phase transition temperature, latent heat of phase change 178J/g) one or more.
6. preparation method according to claim 1, it is characterised in that: the polyether polyol in the step (2) can be
Degree of functionality is 2, the polytetrahydrofuran polyol (PTMG) that molecular weight is 1000 or 2000；Degree of functionality is 2, molecular weight be 1000 or
2000 polycaprolactone polyol (PCL)；Degree of functionality is 2, the polycarbonate polyol (PCD) that molecular weight is 1000 or 2000.
7. preparation method according to claim 1, it is characterised in that: component A and B component need in the step (3)
40 ~ 50 DEG C are previously heated to, it is 1:01.0 ± 0.1 that component A and B component, which use mass ratio, and molar ratio is 1:1.05 ± 0.05.
8. preparation method according to claim 1, it is characterised in that: in the step (3) mold be preheating to 60 in advance ~
70 DEG C, after injecting the polyurethane elastomer raw material of the filler of energy-absorbing containing phase transformation, mold, which is put into 60 ~ 80 DEG C of convection ovens, heats 10-
20 minutes.
9. preparation method according to claim 1, it is characterised in that: it is 100 parts with the quality of polyether polyol and calculates,
The mass content of its each component are as follows:
40-55 parts of polyether polyol
2-8 parts of chain extender
0.1-0.4 parts of chemical foaming agent
0.2-2 parts of foam stabiliser
0.2-2 parts of catalyst
0.5-5 parts of mill base
5-40 parts of phase transformation powder stuffing.
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| CN113461900A (en) * | 2021-07-19 | 2021-10-01 | 北京理工大学 | Low-static-rigidity polyurethane microporous elastic base plate with low-temperature static rigidity change rate |
| CN114181515A (en) * | 2021-12-09 | 2022-03-15 | 北京理工大学 | Preparation method of shock wave resistant polyurethane elastomer |
| CN114516946A (en) * | 2022-03-25 | 2022-05-20 | 北京理工大学 | Outer-layer buffering thermal insulation material for anti-drop impact light protective box |
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| CN113307930A (en) * | 2021-07-19 | 2021-08-27 | 北京理工大学 | Cold-resistant high-static-stiffness polyurethane microporous elastic base plate |
| CN113307940A (en) * | 2021-07-19 | 2021-08-27 | 北京理工大学 | Low-temperature-resistant middle-static-stiffness polyurethane microporous elastic base plate |
| CN113461900A (en) * | 2021-07-19 | 2021-10-01 | 北京理工大学 | Low-static-rigidity polyurethane microporous elastic base plate with low-temperature static rigidity change rate |
| CN113307930B (en) * | 2021-07-19 | 2022-02-11 | 北京理工大学 | Cold-resistant high-static-stiffness polyurethane microporous elastic base plate |
| CN114181515A (en) * | 2021-12-09 | 2022-03-15 | 北京理工大学 | Preparation method of shock wave resistant polyurethane elastomer |
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