CN105860007B - A kind of modified TPU material and preparation method thereof - Google Patents
A kind of modified TPU material and preparation method thereof Download PDFInfo
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- CN105860007B CN105860007B CN201610262681.8A CN201610262681A CN105860007B CN 105860007 B CN105860007 B CN 105860007B CN 201610262681 A CN201610262681 A CN 201610262681A CN 105860007 B CN105860007 B CN 105860007B
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- 239000006247 magnetic powder Substances 0.000 claims abstract description 26
- 239000004970 Chain extender Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 23
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 15
- 229920005906 polyester polyol Polymers 0.000 claims abstract description 14
- 229920005830 Polyurethane Foam Polymers 0.000 claims abstract description 13
- 239000011496 polyurethane foam Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 145
- 239000004433 Thermoplastic polyurethane Substances 0.000 claims description 68
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- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 4
- 150000001298 alcohols Chemical group 0.000 claims description 4
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
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- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 3
- WTPYFJNYAMXZJG-UHFFFAOYSA-N 2-[4-(2-hydroxyethoxy)phenoxy]ethanol Chemical compound OCCOC1=CC=C(OCCO)C=C1 WTPYFJNYAMXZJG-UHFFFAOYSA-N 0.000 claims description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 2
- QWGRWMMWNDWRQN-UHFFFAOYSA-N 2-methylpropane-1,3-diol Chemical compound OCC(C)CO QWGRWMMWNDWRQN-UHFFFAOYSA-N 0.000 claims description 2
- IBOFVQJTBBUKMU-UHFFFAOYSA-N 4,4'-methylene-bis-(2-chloroaniline) Chemical compound C1=C(Cl)C(N)=CC=C1CC1=CC=C(N)C(Cl)=C1 IBOFVQJTBBUKMU-UHFFFAOYSA-N 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 claims description 2
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- 241001112258 Moca Species 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims description 2
- 235000019437 butane-1,3-diol Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229940100573 methylpropanediol Drugs 0.000 claims description 2
- FJJWJAFSUDWTTR-UHFFFAOYSA-N n,n-dihydroxyaniline Chemical compound ON(O)C1=CC=CC=C1 FJJWJAFSUDWTTR-UHFFFAOYSA-N 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920001296 polysiloxane Polymers 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 239000004088 foaming agent Substances 0.000 claims 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical class OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims 1
- 238000005984 hydrogenation reaction Methods 0.000 claims 1
- 150000002513 isocyanates Chemical class 0.000 claims 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims 1
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- QXZGBUJJYSLZLT-FDISYFBBSA-N bradykinin Chemical compound NC(=N)NCCC[C@H](N)C(=O)N1CCC[C@H]1C(=O)N1[C@H](C(=O)NCC(=O)N[C@@H](CC=2C=CC=CC=2)C(=O)N[C@@H](CO)C(=O)N2[C@@H](CCC2)C(=O)N[C@@H](CC=2C=CC=CC=2)C(=O)N[C@@H](CCCNC(N)=N)C(O)=O)CCC1 QXZGBUJJYSLZLT-FDISYFBBSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
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- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 208000029078 coronary artery disease Diseases 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6633—Compounds of group C08G18/42
- C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2101/00—Manufacture of cellular products
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to a kind of modified TPU material, it includes following components and parts by weight：Polyester polyol：30 130 parts by weight, diisocyanate：30 110 parts by weight, dihydric alcohol：8 45 parts by weight, pore-creating agent：3 11 parts by weight, polyurethane foams：5 15 parts by weight, chain extender：3 11 parts by weight, magnetic powder：20 110 parts by weight, the present invention provide a kind of modified TPU material and preparation method thereof, not only have the performance of tradition TPU, but also have the function that magnetic therapy, and the method manufactured is simple, and easy to operate and product is easy to get, and is suitably applied the fields such as household.
Description
Technical field
The present invention relates to TPU Material Fields, more particularly to a kind of modified TPU material and preparation method thereof.
Background technology
TPU (Thermoplastic polyurethanes) entitled thermoplastic polyurethane elastomer rubber.It is broadly divided into
There is point of polyester-type and polyether-type, the features such as it has, and hardness range is wide, wear-resisting, oil resistant, transparent, and elasticity is good, in daily necessities, body
Educate the fields such as articles for use, toy, ornament materials to be used widely, and halogen-free flameproof TPU can also replace flexible PVC to meet
The environmental requirement in more and more fields.At present, product made of in the market TPU materials is more and more, but simply has mostly
The characteristics of TPU is original, it is impossible to meet the needs of market well, in addition, also there is the making side that partial monopoly discloses TPU materials
Method, and the modification to TPU materials, such as application publication number CN103665829A（2014-03-26）Disclosed environment protection high flame resistance heat
Plastic polyurethane method for producing elastomers, the elastomer of preparation maintain excellent lower temperature resistance, pliability and hydrolytic resistance,
And composite halogen-free fire retardant is used, greatly ensure that the excellent performance of elastomer in itself, has not also been produced even if fire burning is met
Raw environmentally harmful gas, can be widely used for the fields such as cable jacket, automobile component and oil hose, but this TPU materials
Material cannot be applied to the fields such as household well.
The content of the invention
Present invention aim to address the above problem, there is provided a kind of modified TPU material and preparation method thereof, not only has and pass
The performance of system TPU, and also there is magnetic therapy, the method simple products of manufacture are easy to get, and are suitably applied household field, special
The mat such as mattress field is not suitably applied.
The present invention above-mentioned technical purpose technical scheme is that：
A kind of modified TPU material, it includes following components and parts by weight：
Polyester polyol：30-130 parts by weight
Diisocyanate：30-110 parts by weight
Dihydric alcohol：8-45 parts by weight
Pore-creating agent：3-11 parts by weight
Polyurethane foams：5-15 parts by weight
Chain extender：3-11 parts by weight
Magnetic powder：20-110 parts by weight
A kind of production method of modified TPU material is as follows：
（1）By the diisocyanate of the polyester polyol of the 30-130 parts by weight and the 30-110 parts by weight add to
In reaction kettle, 80-110 DEG C is heated to, stirring is opened after melting；
（2）Treat step（1）In material mixing completely after add 8-45 parts by weight dihydric alcohol, then keep the temperature 0.5-1h；
（3）60-80 DEG C of cooling, and add the pore-creating agent of 3-11 parts by weight, 5-15 parts by weight for the first time is carried out to reaction kettle
Polyurethane foams, and the chain extender of 3-11 parts by weight stirs evenly, then keeps the temperature 0.5-1.5h；
（4）Vacuumize process is carried out to reaction kettle, second is then carried out and cools down, temperature is to less than 50 DEG C, then blowing；
（5）By step（4）The material of middle releasing is sent into mixer mixing, adds the magnetic powder of 20-110 parts by weight, mixing
Uniformly, mixture is obtained；
（6）By step（5）Described in mixture be sent into plastics processing mill heating plasticizing, by after plasticizing raw material be sent into filtering
Machine, impurity screening, is made raw material；
（7）By step（6）Described in raw material pour into and scribble in advance in the mould of releasing agent；
（8）By step（7）In mould be put into togerther with the raw material in drier, 60-150 DEG C of dry 0.5-2h, so
Modified TPU materials are separated to room temperature and take out modified TPU materials by postcooling with mould.
Manufactured TPU materials are mixed with magnetic powder in this programme, manufactured modified TPU material not only has the performance of TPU,
Also add the effect of magnetic powder so that manufactured modified TPU material hardness scope is wide, wear-resisting, oil resistant, transparent, and elasticity is good, and
There is magnetic therapy, can be adapted for the fields such as daily necessities, sports goods, toy, ornament materials.In prepared by industrial production,
If paid no heed to, temperature height is uneven to be easy to the phenomenon that local solidification causes whole materials changes to be given up occur, metal material
Addition, which is more easily led to, there is the probability solidified in TPU manufacturing process, and contains metallic element or metal oxide in magnetic powder, in life
In production, it is also bigger to solidify the probability of generation, this is also that other producers control bad technique, it is impossible to the reason for batch making, but
It is to solve the problems, such as this well by the improvement to technique in this programme so that modified TPU material can be fine with magnetic powder
Mixing, and do not interfere with the performance of TPU, it is excellent will not to have security risk, the manufactured modified TPU material properties such as solidification
More, can be produced with bulk industrial, in addition, with TPU quote it is extensive, traditional TPU performances are not well positioned to meet
Modernization, intensive requirement, magnetic powder and tradition TPU, which are combined, can make modified TPU material have more use value, and magnetic
Treatment is increasingly received by the mankind now, more convenient to use, more can provide curative effect for the health of the mankind.
The effect of magnetic therapy is as follows：
1. magnetic therapy can strengthen the vitality of white blood cell, under the influence of a magnetic field, white blood cell phagocytosis function is more active, red blood
The sedimentation of ball and lymphocyte is slack-off, is conducive to anti-inflammatory and reduces erythrocyte sedimentation rate.
2. magnetic therapy can improve blood circulation, strengthen the absorption of oxygen and irony, exclude the dirt in carbon dioxide and blood
Deng harmful toxins and fatigue substances.
3. magnetic therapy can produce electric current in vivo, the elasticity for increasing vascular wall distends the blood vessels, and reduces blood viscosity, accelerates blood
Stream, eliminates embolism.
4. magnetic therapy, which has, strengthens endocrine liquid osmosis, endocrine imbalance and disorder are corrected.
5. magnetic therapy can stimulate the inductor of human body -- excited nerve ending, adjusts nervous function.
6. magnetic therapy can spread and disappear algogenic substance such as bradykinin, 5- tryptamines, acidic metabolite etc., mitigate and eliminate
Pain.
And clinically it has proven convenient that the disease that every Traditional Chinese medicine blood circulation promoting silt therapy can treat, magnetic therapy can treat greatly,
And effect is fine, such as hemotoncus, hypertension, headstroke, coronary heart disease, diabetes, hydrothorax, ephritis, oedema, especially joint
Pain etc. all receives good effect, and the effect to activate blood circulation and disperse blood clots for illustrating magnetic therapy is very strong.
Step described in this programme（2）Middle insulation is in order to preferably by the dihydric alcohol and the step（1）In it is mixed
Compound progress hybrid reaction, and the step（3）In insulation be in order to by pore-creating agent, polyurethane foams and chain extender incorporate
In reactant, mixed, the step（3）Described in first time cooling also allow for the pore-creating agent, polyurethane hair
The characteristic of infusion and chain extender, if temperature is excessive, then the addition of the pore-creating agent, polyurethane foams and chain extender can make
The polymerization of reactant is obtained, solidification phenomenon occurs, security risk can more occur for severe one, so first time cooling is particularly significant,
And step（4）In second cooling be then for convenience finishing operations personnel material filling operate, temperature is excessive, and blowing is dangerous
And material touches metal bucket also can be there is a phenomenon where solidifying, therefore first time cooling and second of cooling can avoid
Material is scrapped；The step（4）In cooling also have one it is important the reason for be exactly later stage and the magnetic powder for convenience
With reference to, the low stabilization for contributing to material performance of temperature, the step（6）It is middle by step（5）Described in mixture be sent into refining modeling
Machine heating plasticizing, send the raw material after plasticizing into filter, impurity screening is to make the modified TPU material hardness model after making
Wide, wear-resisting, oil resistant is enclosed, transparent, elasticity is good, smooth, and has the function that magnetic therapy.
Preferably, the polyester polyol is polyethylene glycol adipate glycol, polybutylene glyool adipate, gathers
Adipate glycol-one or both of butyl glycol ester diol or polyhexamethylene adipate glycol.
Preferably, the dihydric alcohol includes ethylene glycol, 1,2- propane diols, Isosorbide-5-Nitrae-butanediol, methyl propanediol, 1,3-
Butanediol, diglycol, 1, the one or more of 6- hexylene glycols or neopentyl glycol.
Preferably, the diisocyanate include toluene di-isocyanate(TDI), 4,4 '-methyl diphenylene diisocyanate,
Hydrogenate 4,4 '-methyl diphenylene diisocyanate, 1,6- hexylidene diisocyanates, one kind of isophorone diisocyanate
It is or a variety of.
Preferably, the pore-creating agent includes polypropylene oxide-ethylene oxide copolyether, one polysiloxanes of polyoxygenated alkene
One or more in copolymer.Pore-creating agent is a kind of special surfactant, its effect is to reduce the surface of foam
Power;Promote blasthole to rupture, improve the percent opening of polyurethane foam plastics, improve soft caused by closed pore.
Preferably, the step（4）The middle pumpdown time is 10-45min, and pressure is（-0.08）-（-0.09）MPa.
The setting vacuumized, is to allow the mixture to react more rapid, while ensureing to keep the safety in production, reduce and give birth to
Produce the cycle.
Preferably, the chain extender is the one or more in alcohols chain extender or amine chain extender, the alcohols expands
Chain agent includes glycerine, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, neopentyl glycol, sorbierite, diethylaminoethanol；The amine
Chain extender includes MOCA, ethylenediamine, N, N- dihydroxy aniline, HQEE.The setting of the chain extender be in order to linear polymerization
Functional group reactions on thing chain and make strand extension, molecular weight increase, to improve polyurethane, polyester mechanical property and craftsmanship
Energy.
Preferably, the magnetic powder is permanent magnetism powder, the preparation method of the permanent magnetism powder is as follows：
（a）To permanent-magnet material carry out melting, control vacuum between 1-4pa, smelting temperature between 750-1600 DEG C,
Obtain aluminium alloy；
（b）Using vacuum induction formula fast quenching or vacuum arc formula fast quenching to step（a）Described in aluminium alloy carry out fast quenching,
The linear velocity of fast quenching is 20-35m/s, obtains alloy thin band；
（c）Between 550-750 DEG C and under vacuum conditions to step（b）Described in alloy thin band be heat-treated, heat
Processing time is 10-30min；
（d）To step（c）Alloy thin band after middle heat treatment is crushed, and obtains alloyed powder,
（e）To step（d）Described in alloyed powder carry out postprocessing working procedures, conjunction of the screening granularity between 160-200um
Bronze obtains permanent magnetism powder.
This method prepare permanent magnetism powder, non-magnetic phase is few, and crystal grain is small, and component is uniform, and alloying component processing range is wide, compared with
Preferable alloy structure can be obtained under wide process conditions.The step（b）It is in order to obtain that the linear velocity of middle fast quenching, which is set,
Alloy thin band it is more uniform, unification degree is high, and thickness is controlled, and step（c）In the alloy thin band is heat-treated
It is to allow the alloy thin band rapid curing, the technique for facilitating the later stage, reduces the production cycle, reduces production cost.
Preferably, state step（6）The filtering mesh of middle filter is -160 mesh of 100 mesh.
Preferably, the step（5）The temperature setting of middle mixer mixing is between 115 DEG C -130 DEG C, the step
（6）The temperature of middle plastics processing mill heating plasticizing is 135 DEG C -150 DEG C.
In conclusion the invention has the advantages that：
1st, a kind of modified TPU material provided by the invention and preparation method thereof, technique is simple, and product is easy to get, and is not in
Phenomena such as overflowing pot, solidification, and for manufacturing product, have that hardness range is wide, wear-resisting, oil resistant, transparent, elastic good, reproducibility
The features such as strong, conveniently mould；
2nd, a kind of modified TPU material provided by the invention and preparation method thereof, product made of the modified TPU material of use
The function of magnetic therapy, can treat some diseases of human body, protect the health of human body.
Embodiment
This specific embodiment is only explanation of the invention, it is not limitation of the present invention, people in the art
Member as needed can make the present embodiment the modification of no creative contribution after this specification is read, but as long as at this
All protected in the right of invention be subject to Patent Law.
Formula one：
Polyester polyol：30 parts by weight, diisocyanate：30 parts by weight, dihydric alcohol：8 parts by weight, pore-creating agent：3 weights
Measure part, polyurethane foams：5 parts by weight, chain extender：3 parts by weight, magnetic powder：20 parts by weight；
Formula two
Polyester polyol：130 parts by weight, diisocyanate：110 parts by weight, dihydric alcohol：45 parts by weight, pore-creating agent：
11 parts by weight, polyurethane foams：15 parts by weight, chain extender：11 parts by weight, magnetic powder：110 parts by weight；
Formula three
Polyester polyol：100 parts by weight, diisocyanate：80 parts by weight, dihydric alcohol：35 parts by weight, pore-creating agent： 7
Parts by weight, polyurethane foams：12 parts by weight, chain extender：7 parts by weight, magnetic powder：70 parts by weight.
Embodiment 1
A kind of modified TPU material is prepared using formula one, its production method is as follows：
（1）Polyester polyol and diisocyanate are added to reaction kettle, are heated to 80 DEG C, stirring is opened after melting；
（2）Treat step（1）In material mixing completely after add dihydric alcohol, then keep the temperature 0.5h;
（3）60 DEG C of cooling, and add pore-creating agent for the first time, polyurethane foams, and chain extender are carried out to reaction kettle, stirred
Mix uniformly, then keep the temperature 0.5h；
（4）Vacuumize process is carried out to reaction kettle, pumpdown time 10min, pressure is -0.08MPa, then carries out the
Reducing temperature twice, temperature are down to less than 50 DEG C, then blowing；
（5）By step（4）The material of middle releasing is sent into mixer mixing, the temperature setting of mixer mixing at 115 DEG C,
Magnetic powder is added, is uniformly mixed, obtains mixture；
（6）By step（5）In mixture be sent into plastics processing mill heating plasticizing, plastics processing mill heating plasticizing temperature be 135
DEG C, the raw material after plasticizing is sent into filter, the filtering mesh of filter is 160 mesh, and impurity screening, is made raw material；
（7）By step（6）In raw material pour into and scribble in advance in the mould of releasing agent；
（8）By step（7）In mould be put into togerther with raw material in drier, 60 DEG C of dry 2h, are subsequently cooled to room temperature,
Modified TPU materials are separated with mould and take out modified TPU materials.
Magnetic powder is permanent magnetism powder, and the preparation method of permanent magnetism powder is as follows：
（a）Melting is carried out to permanent-magnet material, control vacuum obtains aluminium alloy in 4pa, smelting temperature at 750 DEG C；
（b）Using vacuum induction formula fast quenching or vacuum arc formula fast quenching to step（a）Middle aluminium alloy carries out fast quenching, fast quenching
Linear velocity be 20m/s, obtain alloy thin band；
（c）At 750 DEG C and under vacuum conditions to step（b）Middle alloy thin band is heat-treated, and heat treatment time is
10min；
（d）To step（c）Alloy thin band after middle heat treatment is crushed, and obtains alloyed powder,
（e）To step（d）In alloyed powder carry out postprocessing working procedures, screening granularity 160um alloyed powder i.e. obtain forever
Magnetic powder.
Embodiment 2
A kind of modified TPU material is prepared using formula two, its production method is as follows：
（1）Polyester polyol and diisocyanate are added to reaction kettle, are heated to 110 DEG C, stirring is opened after melting；
（2）Treat step（1）In material mixing completely after add dihydric alcohol, then keep the temperature 1h;
（3）80 DEG C of cooling, and add pore-creating agent for the first time, polyurethane foams, and chain extender are carried out to reaction kettle, stirred
Mix uniformly, then keep the temperature 1.5h；
（4）Vacuumize process is carried out to reaction kettle, pumpdown time 45min, pressure is -0.09MPa, then carries out the
Reducing temperature twice, temperature are down to less than 50 DEG C, then blowing；
（5）By step（4）The material of middle releasing is sent into mixer mixing, the temperature setting of mixer mixing at 130 DEG C,
Magnetic powder is added, is uniformly mixed, obtains mixture；
（6）By step（5）In mixture be sent into plastics processing mill heating plasticizing, plastics processing mill heating plasticizing temperature be 150
DEG C, the raw material after plasticizing is sent into filter, the filtering mesh of filter is 100 mesh, and impurity screening, is made raw material；
（7）By step（6）In raw material pour into and scribble in advance in the mould of releasing agent；
（8）By step（7）In mould be put into togerther with raw material in drier, 150 DEG C of dry 0.5h, are subsequently cooled to
Room temperature, modified TPU materials are separated with mould and take out modified TPU materials.
Magnetic powder is permanent magnetism powder, and the preparation method of permanent magnetism powder is as follows：
（a）Melting is carried out to permanent-magnet material, control vacuum obtains aluminium alloy in 1pa, smelting temperature at 1600 DEG C；
（b）Using vacuum induction formula fast quenching or vacuum arc formula fast quenching to step（a）Middle aluminium alloy carries out fast quenching, fast quenching
Linear velocity be 35m/s, obtain alloy thin band；
（c）At 550 DEG C and under vacuum conditions to step（b）Middle alloy thin band is heat-treated, and heat treatment time is
30min；
（d）To step（c）Alloy thin band after middle heat treatment is crushed, and obtains alloyed powder,
（e）To step（d）In alloyed powder carry out postprocessing working procedures, screening granularity 200um alloyed powder i.e. obtain forever
Magnetic powder.
Embodiment 3
A kind of modified TPU material is prepared using formula three, its production method is as follows：
（1）Polyester polyol and diisocyanate are added to reaction kettle, are heated to 100 DEG C, stirring is opened after melting；
（2）Treat step（1）In material mixing completely after add dihydric alcohol, then keep the temperature 0.8h;
（3）70 DEG C of cooling, and add pore-creating agent for the first time, polyurethane foams, and chain extender are carried out to reaction kettle, stirred
Mix uniformly, then keep the temperature 1h；
（4）Vacuumize process is carried out to reaction kettle, pumpdown time 25min, pressure is -0.085MPa, is then carried out
Second of cooling, temperature are down to less than 50 DEG C, then blowing；
（5）By step（4）The material of middle releasing is sent into mixer mixing, the temperature setting of mixer mixing at 125 DEG C,
Magnetic powder is added, is uniformly mixed, obtains mixture；
（6）By step（5）In mixture be sent into plastics processing mill heating plasticizing, plastics processing mill heating plasticizing temperature be 145
DEG C, the raw material after plasticizing is sent into filter, the filtering mesh of filter is 130 mesh, and impurity screening, is made raw material；
（7）By step（6）In raw material pour into and scribble in advance in the mould of releasing agent；
（8）By step（7）In mould be put into togerther with raw material in drier, 120 DEG C of dry 1h, are subsequently cooled to room
Temperature, modified TPU materials are separated with mould and take out modified TPU materials.
Magnetic powder is permanent magnetism powder, and the preparation method of permanent magnetism powder is as follows：
（a）Melting is carried out to permanent-magnet material, control vacuum obtains aluminium alloy in 3pa, smelting temperature at 1300 DEG C；
（b）Using vacuum induction formula fast quenching or vacuum arc formula fast quenching to step（a）Middle aluminium alloy carries out fast quenching, fast quenching
Linear velocity be 30m/s, obtain alloy thin band；
（c）At 650 DEG C and under vacuum conditions to step（b）Middle alloy thin band is heat-treated, and heat treatment time is
23min；
（d）To step（c）Alloy thin band after middle heat treatment is crushed, and obtains alloyed powder,
（e）To step（d）In alloyed powder carry out postprocessing working procedures, screening granularity 175um alloyed powder i.e. obtain forever
Magnetic powder.
Comparative example 1
With embodiment 2, difference is comparative example 1：
Step（1）It is middle to add polyester polyol and diisocyanate to reaction kettle, 160 DEG C are heated to, is opened after melting
Open stirring；
Step（4）In to reaction kettle carry out vacuumize process, pumpdown time 70min, pressure is -0.75MPa.
Comparative example 2
With embodiment 2, difference is comparative example 1：
（a）Melting is carried out to permanent-magnet material, control vacuum obtains aluminium alloy in 7pa, smelting temperature at 700 DEG C；
（b）Using vacuum induction formula fast quenching or vacuum arc formula fast quenching to step（a）Middle aluminium alloy carries out fast quenching, fast quenching
Linear velocity be 10m/s, obtain alloy thin band；
（c）At 650 DEG C and under vacuum conditions to step（b）Middle alloy thin band is heat-treated, and heat treatment time is
23min；
（d）To step（c）Alloy thin band after middle heat treatment is crushed, and is obtained alloyed powder, that is, is obtained permanent magnetism powder
Modified TPU material is prepared with embodiment in above 5 respectively, and mattress is made, observation prepares live phenomenon, and uses
Mattress as a result, record it is as follows：
| Embodiment | Prepare scene and use result |
| Embodiment 1 | It is smooth to prepare modified TPU materials process, manufactured modified TPU material hardness scope is wide, wear-resisting, oil resistant, transparent, and elasticity is good, and manufactured mattress has good magnetic therapy effect using comfortably. |
| Embodiment 2 | It is smooth to prepare modified TPU materials process, manufactured modified TPU material hardness scope is wide, wear-resisting, oil resistant, transparent, and elasticity is good, and manufactured mattress has good magnetic therapy effect using comfortably. |
| Embodiment 2 | It is smooth to prepare modified TPU materials process, manufactured modified TPU material hardness scope is wide, wear-resisting, oil resistant, transparent, and elasticity is good, and manufactured mattress has good magnetic therapy effect using comfortably. |
| Comparative example 1 | Overflowing pot phenomenon occurs when preparing TPU materials, material largely loses, and when vacuumizing, solidification phenomenon occurs. |
| Comparative example 2 | When making magnetic powder, aluminium alloy the coexisting body alloy thin band of amorphous and crystallite can not be made by fast quenching, manufactured mattress surface is coarse, and uses discomfort with the presence of the phenomenon substantially aoxidized. |
As seen from the above table, modified TPU material can be successfully made in embodiment 1, embodiment 2 and embodiment 3, and uses
Mattress made of modified TPU material has good magnetotherapy effect, and comfort level is good, and hardness range is wide, wear-resisting, oil resistant, thoroughly
Bright, elasticity is good, and comparative example 1 is clearly present deficiency during operation, it is impossible to good modified TPU material is made；
Permanent magnet size made of comparative example 2 is uneven, and is aoxidized, and does not have or has less magnetotherapy effect, cannot all expire
The demand of sufficient in the market, the technique of this programme can made of modified TPU material, and manufactured modified TPU material can meet
The market demand.
Claims (9)
- A kind of 1. modified TPU material, it is characterised in that：It includes following components and parts by weight：Polyester polyol：30-130 parts by weightDiisocyanate：30-110 parts by weightDihydric alcohol：8-45 parts by weightPore-creating agent：3-11 parts by weightPolyurethane foams：5-15 parts by weightChain extender：3-11 parts by weightMagnetic powder：20-110 parts by weightA kind of production method of modified TPU material is as follows：（1）The diisocyanate of the polyester polyol of the 30-130 parts by weight and the 30-110 parts by weight is added to reaction In kettle, 80-110 DEG C is heated to, stirring is opened after melting；（2）Treat step（1）In material mixing completely after add 8-45 parts by weight dihydric alcohol, then keep the temperature 0.5-1h；（3）60-80 DEG C of cooling, and add the pore-creating agent of 3-11 parts by weight for the first time is carried out to reaction kettle, 5-15 parts by weight are gathered Urethane foaming agent, and the chain extender of 3-11 parts by weight, stir evenly, then keep the temperature 0.5-1.5h；（4）Vacuumize process is carried out to reaction kettle, second is then carried out and cools down, temperature is to less than 50 DEG C, then blowing；（5）By step（4）The material of middle releasing is sent into mixer mixing, adds the magnetic powder of 20-110 parts by weight, and mixing is equal It is even, obtain mixture；（6）By step（5）Described in mixture be sent into plastics processing mill heating plasticizing, by after plasticizing raw material be sent into filter, mistake Impurity is filtered, intermediate raw material is made；（7）By step（6）Described in intermediate raw material pour into and scribble in advance in the mould of releasing agent；（8）By step（7）In mould be put into togerther with the intermediate raw material in drier, 60-150 DEG C of dry 0.5-2h, so Modified TPU materials are separated to room temperature and take out modified TPU materials by postcooling with mould；The magnetic powder is permanent magnetism powder, and the preparation method of the permanent magnetism powder is as follows：（a）Melting is carried out to permanent-magnet material, between 1-4pa, smelting temperature obtains control vacuum between 750-1600 DEG C Aluminium alloy；（b）Using vacuum induction formula fast quenching or vacuum arc formula fast quenching to step（a）Described in aluminium alloy carry out fast quenching, fast quenching Linear velocity be 20-35m/s, obtain alloy thin band；（c）Between 550-750 DEG C and under vacuum conditions to step（b）Described in alloy thin band be heat-treated, be heat-treated Time is 10-30min；（d）To step（c）Alloy thin band after middle heat treatment is crushed, and obtains alloyed powder,（e）To step（d）Described in alloyed powder carry out postprocessing working procedures, alloyed powder of the screening granularity between 160-200um Obtain permanent magnetism powder.
- A kind of 2. modified TPU material according to claim 1, it is characterised in that：The polyester polyol is polyadipate Glycol ester glycol, polybutylene glyool adipate, polyadipate ethylene glycol-butyl glycol ester diol or polyadipate oneself two One or both of alcohol esterdiol.
- A kind of 3. modified TPU material according to claim 2, it is characterised in that：The dihydric alcohol includes ethylene glycol, 1,2- Propane diols, Isosorbide-5-Nitrae-butanediol, methyl propanediol, 1,3- butanediols, diglycol, 1,6- hexylene glycols or neopentyl glycol One or more.
- A kind of 4. modified TPU material according to claim 3, it is characterised in that：The diisocyanate includes toluene two Isocyanates, 4,4 '-methyl diphenylene diisocyanate, 4,4 '-methyl diphenylene diisocyanate of hydrogenation, 1,6- it is sub- oneself The one or more of group diisocyanate, isophorone diisocyanate.
- A kind of 5. modified TPU material according to claim 1, it is characterised in that：The pore-creating agent include polypropylene oxide- One or more in ethylene oxide copolyether, one polysiloxane copolymer of polyoxygenated alkene.
- A kind of 6. modified TPU material according to claim 1, it is characterised in that：The step（4）The middle pumpdown time is 10-45min, pressure are（-0.08）-（-0.09）MPa.
- A kind of 7. modified TPU material according to claim 1, it is characterised in that：The chain extender for alcohols chain extender or One or more in amine chain extender, the alcohols chain extender include glycerine, trimethylolpropane, diethylene glycol (DEG), triethylene glycol, new Pentanediol, sorbierite, diethylaminoethanol；The amine chain extender include MOCA, ethylenediamine, N, N- dihydroxy aniline, HQEE。
- A kind of 8. modified TPU material according to claim 1, it is characterised in that：State step（6）The filter screen of middle filter Mesh is -160 mesh of 100 mesh.
- A kind of 9. modified TPU material according to claim 1, it is characterised in that：The step（5）Middle mixer mixing Temperature setting is between 115 DEG C -130 DEG C, the step（6）The temperature of middle plastics processing mill heating plasticizing is 135 DEG C -150 DEG C.
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| CN103588944A (en) * | 2013-10-29 | 2014-02-19 | 中国科学院长春应用化学研究所 | Damping-adjustable polyurethane material and its preparation method and application thereof |
| CN104592477A (en) * | 2015-02-16 | 2015-05-06 | 中北大学 | Preparation method of high-performance magnetic polyurethane elastomer composites |
| CN104599834A (en) * | 2015-01-17 | 2015-05-06 | 浙江和也健康科技有限公司 | Manufacturing method for thermoplastic compound macromolecule bonded magnet |
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| CN103588944A (en) * | 2013-10-29 | 2014-02-19 | 中国科学院长春应用化学研究所 | Damping-adjustable polyurethane material and its preparation method and application thereof |
| CN104599834A (en) * | 2015-01-17 | 2015-05-06 | 浙江和也健康科技有限公司 | Manufacturing method for thermoplastic compound macromolecule bonded magnet |
| CN104592477A (en) * | 2015-02-16 | 2015-05-06 | 中北大学 | Preparation method of high-performance magnetic polyurethane elastomer composites |
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