CN109943907A - A kind of preparation method of magnetic polyurethane elastomer - Google Patents
A kind of preparation method of magnetic polyurethane elastomer Download PDFInfo
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- CN109943907A CN109943907A CN201910093057.3A CN201910093057A CN109943907A CN 109943907 A CN109943907 A CN 109943907A CN 201910093057 A CN201910093057 A CN 201910093057A CN 109943907 A CN109943907 A CN 109943907A
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- polyurethane elastomer
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Abstract
The present invention relates to a kind of preparation methods of magnetic polyurethane elastomer, this method prepares the finely dispersed magnetic slurry solution of magnetic powder by grinding emulsification, magnetic polyurethane spinning solution is made in pulp solution incorporation polyether polyols, then the spinning solution is prepared into final magnetic polyurethane elastomer using dry spinning；Wherein: polyether polyols are performed polymer to be formed by polyetherdiol, diisocyanate ester condensation addition polymerization, then the performed polymer, diamine, the common chain extension of chain terminating agent are formed.Polyurethane elastomeric fiber using the method preparation has good magnetic property, magnetic fibre Safety and Environmental Protection is good, the adjustable vivo biodistribution magnetic field of the fabric knitted generates induction micro-current, changes permeability of cell membrane, the activity for changing certain enzymes and expansion blood vessel, accelerates blood flow, thus reach such as relieve pain, auxiliary therapeutic action of reducing swelling.
Description
Technical field
The present invention relates to a kind of preparation methods of magnetic polyurethane elastomer.
Background technique
Polyurethane elastomeric fiber is a kind of conjunction with excellent properties such as high extension at break, low modulus and elastic recovery rates
At fiber, it is widely used in the fields such as knitted apparel, household items.Development and human lives' water with global economy society
Flat, safety and environmental protection consciousness increasingly raising, it is fine to safe and healthy, environmentally protective new polyurethane elasticity with property
The demand of dimension is more strong.
Magnetic therapy is a kind of ancient adjuvant treatment measure, has lot of documents to be reported both at home and abroad, the mankind are all the time
It does not live in earth magnetic field, astronaut is in space due to the effect in disengaging earth magnetic field, it is possible to it is comprehensive to there is initiation space
Close the risk of disease, it can be seen that importance of the magnetic for life.Medical magnetic therapy has five major class, is magnetostatic, dynamic magnetic, perseverance respectively
Magnetic, magnetized water and needle etc. can improve the nutrition of blood tissues, pain caused by overcoming because of histanoxia, iron deficiency, nerve endings
Bitterly, analgesic activity is played, magnetic therapy can be used to mitigate pain in functional pain such as DOMS etc..On May 11st, 2011,
" the magnetic therapy equipment registration technological audit guideline " of state food pharmaceuticals administration general bureau publication proposes, " it is now recognized that magnetic
The adjustable vivo biodistribution magnetic field in field, the activity and expansion generate induction micro-current, change permeability of cell membrane, changing certain enzymes
Blood vessel, accelerate blood flow, thus reach such as relieve pain, auxiliary therapeutic action of reducing swelling ".
In view of the special efficacy of magnetic therapy, assigns various types of materials magnetism and become as the target of numerous researchers, by research,
It develops and has magnetic various product, searches out the class that all kinds of production methods of imparting magnetism of material are persistently studied as everybody
Topic.Assign at present magnetic more matrix resin focus mostly on viscose glue, polyester, polypropylene, polyamide, polyacrylonitrile, polylactic acid,
Cellulose etc. (CN1252460A, CN107142553A, CN102330176A, CN1279228C, CN1078634C)；Molding side
Fado concentrates on the preparation of the matrix resin particles containing magnetic and by screw extruder melting extrusion at fiber or by being kneaded tabletting
Product colour is protected to magnetic particle of becoming a useful person and changed to machine tabletting at sheet material, by modes such as skin-core structure, epidermis claddings
(CN107177900A,CN108251915A,CN108286085A,CN100543199C)；By chemical modification and with other spies
The shared premixs such as different material such as cellulose, graphene, reach evenly dispersed in matrix and keep matrix strength etc.
(CN102978728A、CN104592477B)。
It is through inspection information it can be found that very rare for the magnetic modified document of polyurethane elastomer progress, further
It is even more to be rarely reported that magnetic polyurethane elastomer, which is spun into polyurethane elastomeric fiber,.
Summary of the invention
Technical problem: the present invention relates to a kind of preparation methods of magnetic polyurethane elastomer, using the method preparation
Polyurethane elastomeric fiber has good magnetic property, and fiber Safety and Environmental Protection is good, the adjustable vivo biodistribution of the fabric knitted
Magnetic field generates induction micro-current, changes permeability of cell membrane, the activity for changing certain enzymes and expansion blood vessel, accelerates blood flow, thus
Reach such as relieve pain, auxiliary therapeutic action of reducing swelling.
Technical solution: a kind of preparation method of magnetic polyurethane elastomer of the invention prepares magnetic powder by grinding emulsification
Magnetic polyurethane spinning solution is made in pulp solution incorporation polyether polyols by finely dispersed magnetic slurry solution, then
The spinning solution is prepared into final magnetic polyurethane elastomer using dry spinning；Wherein: polyether polyols are by gathering
Ether glycol, diisocyanate ester condensation addition polymerization form performed polymer, then the performed polymer, diamine, the common chain extension of chain terminating agent are formed.
The magnetic powder is iron oxide magnetic powder γ-Fe2O3, the modified iron oxide of the method through overdoping, absorption, infiltration, cladding
Magnetic powder, chromium dioxide magnetic powder CrO2, metal magnetic and barium ferrite magnetic powder, magnetic powder size controlling account for magnetic in < 1um, the magnetic powder
Property polyurethane elastomeric fiber weight ratio be 2%-10%, few fibers magnetize magnetic to assign fiber.
The solvent is n,N-Dimethylformamide DMF, n,N-dimethylacetamide DMAC or N, N- diethylformamide
The amides homologue of DEF.
The magnetic slurry solution is that magnetic powder and polyether polyols and auxiliary material are made by grinder grinding emulsification, institute
Stating auxiliary material includes antioxidant, color inhibition agent, lubricant, ultraviolet absorbing agent.
The polyetherdiol is that polytetrahydrofuran diol, polyoxygenated olefin diols or copolyether glycol, polyetherdiol have
The molecular weight of 1000-5000.
The diisocyanate is methyl diphenylene diisocyanate MDI, toluene di-isocyanate(TDI) TDI, naphthalene diisocyanate
Ester NDI, hexamethylene diisocyanate HDI, poly methylene poly phenyl poly isocyanate PAPI or 4,4, one dicyclohexyl methyl hydride
Diisocyanate HMDI；In the performed polymer, diisocyanate end moieties mass percent accounts for the 1.6- of performed polymer
3.0%.
The diamine is ethylenediamine UE, propane diamine UA, 1- methyl-1,5- pentanediamine SPA, hexamethylene diamine or p-phenylenediamine；
The chain terminating agent includes diethylamine ST, n-butanol UB.
In polyether polyols, (dihydric alcohol terminal hydroxy group molal quantity++ 1/2 chain terminating agent of diamine Amino End Group molal quantity rubs
That number)/isocyanate groups molal quantity=1.01-1.05；When chain extension, binary amine end groups molal quantity/chain terminating agent end group mole
Number=12.5-21.0.
The magnetic polyurethane spinning solution has the number-average molecular weight of 40000-500000.
The magnetic polyurethane spinning solution mass concentration is 30-45%.
Magnetic polyurethane elastomer denier is 20D, 30D, 40D, 140D, 840D, 1120D.
The utility model has the advantages that the present invention relates to a kind of magnetic polyurethane elastomer and preparation method thereof, it can using the method
Effectively prepare a kind of magnetic polyurethane elastomer.The innovative point of this method is, carries out grinding cream to magnetic powder by grinder
Change, dispersed-powder is made to be pre-dispersed in the magnetic slurry solution for being made stable in polyether polyols, so that magnetic powder is poly- in rear road
Further dispersion in urethane polymers, prevents magnetic powder from reuniting；It is passed through by participating in magnetic slurry solution in polyether polyols
The magnetic polyurethane elastomeric fiber of tool has been made in dry spinning for the first time.The magnetic polyurethane elastomer prepared by the method
Good with excellent magnetism, fiber Safety and Environmental Protection, the adjustable vivo biodistribution magnetic field of the fabric knitted reaches as relieved pain, disappearing
It is swollen to wait auxiliary therapeutic actions, economic value with higher.
Specific embodiment
A kind of preparation method of magnetic polyurethane elastomer of the invention emulsifies obtained magnetic powder by grinding and is uniformly dispersed
Pulp solution (auxiliary material solution), magnetic polyurethane spinning solution and original is made according to polyether polyols are participated in pulp solution
Three master operation of liquid dry spinning is made, and feature includes:
1. the magnetic powder is iron oxide magnetic powder (γ-Fe2O3), through sides such as overdoping, absorption, infiltration, the certain elements of cladding
The modified iron oxide magnetic powder of method, chromium dioxide magnetic powder (CrO2), the magnetic powders such as metal magnetic and barium ferrite, preferably iron oxide magnetic
Powder, magnetic powder size controlling is in < 1um.
2. the solvent is n,N-Dimethylformamide DMF, n,N-dimethylacetamide DMAC, N, N- diethylformamide
The amides homologue such as DEF, preferably DMAC.
3. the magnetic slurry solution is that magnetic powder and polyether polyols and other auxiliary materials are emulsified by grinder grinding
It is made, it is in order to which magnetic powder is more uniformly pre-dispersed in polyether polyols that polyether polyols are added in pulp solution
In, in favor of further dispersion of the magnetic powder in rear road polyether polyols, prevent magnetic powder from reuniting.Other auxiliary material additives include
Antioxidant, color inhibition agent, lubricant, ultraviolet absorbing agent.
4. the polyetherdiol is polytetrahydrofuran diol, polyoxygenated olefin diols or copolyether glycol, polyetherdiol tool
There are the molecular weight of 1000-5000, preferably polytetrahydrofuran diol, molecular weight preferably 1800 ± 30.
5. the diisocyanate is methyl diphenylene diisocyanate MDI, toluene di-isocyanate(TDI) TDI, two isocyanide of naphthalene
Acid esters NDI, hexamethylene diisocyanate HDI, poly methylene poly phenyl poly isocyanate PAPI or 4,4, one dicyclohexyl first
Alkane diisocyanate HMDI, preferably MDI.
6. in the performed polymer, terminal isocyanate groups group mass percent accounts for the 1.6-3.0% of performed polymer, preferably 2.5-
2.7%.
7. the diamine is ethylenediamine UE, propane diamine UA, 1- methyl-1,5- pentanediamine SPA, hexamethylene diamine or to benzene two
Amine；The chain terminating agent includes diethylamine ST, n-butanol UB.
8. in polyether polyols, (dihydric alcohol terminal hydroxy group molal quantity++ 1/2 chain of diamine Amino End Group molal quantity
Terminator molal quantity)/isocyanate groups molal quantity=1.01-1.05；When chain extension, binary amine end groups molal quantity/
Chain terminating agent end group molal quantity=12.5-21.0, preferably 13-15%.
9. the magnetic polyurethane spinning solution has the number-average molecular weight of 40000-500000, preferably 90000-
250000。
10. the magnetic polyurethane spinning solution mass concentration is 30-45%, preferably 35-37%；
11. the magnetic polyurethane elastomer be made of using dry spinning technology, fiber Denier 20D, 30D,
40D、140D、840D、1120D。
12. the ratio that the magnetic powder accounts for magnetic polyurethane elastomer is 2%-10%, preferably 3-5%, few fibers need to
It magnetizes to assign fiber magnetism.
The following exemplary only case study on implementation of case study on implementation, the claimed range of this patent are not limited to that.
Comparative sample: the preparation of comparative sample
Emulsify the preparation of pulp solution: by 600g solvent DMAC, 18.1g anti-yellowing agent UDT, 36.2g anti ultraviolet agent UTP,
Antioxidant solution SAS172.4g (mass concentration 33.5%), antioxidant CY26.5g lubricate reeling agent magnesium stearate 35g,
101g polyether polyols (mass concentration 36%) are added in grinder, circular grinding 5h, and the finely dispersed emulsification of auxiliary material is made
Pulp solution.
The preparation of polyurethane spinning solution: 5.27Kg solvent dimethyl acetamide (DMAC) metering is entered into pre-reactor
(RA1), stirring is opened, addition 9.50Kg polytetrahydrofuran ether glycol (PTMEG, number-average molecular weight 1810), water-bath are cold into RA1
But 2.20Kg methyl diphenylene diisocyanate (MDI) is added into RA1 after constant temperature 15min to 23 DEG C in reaction kettle, reaction
After 10min, heating water bath pre-reactor is to 45 DEG C and isothermal reaction 2h obtains performed polymer PPS.PPS transfer is entered into chain extending reaction kettle
(RA2) in, 11.4Kg solvent DMAC is added into RA1, after cleaning RA1 5min, solvent transfer is entered into RA2, opens stirring,
Cooling RA2 to 9 DEG C and constant temperature 30min of refrigerant.Chain extension amine aqueous solution is added dropwise into RA2, preceding 75% chain extension amine aqueous solution drop rate is
50g/20s, rear 25% chain extension amine aqueous solution drop rate are 15g/20s, and to control reaction rate, wherein chain extension amine aqueous solution quality is dense
Degree is 5.45%, and group becomes 167.5gUE+68.9gUA+39.9gST+4793.0gDMAC.After being added dropwise to complete, it is added into RA2
It polymerize chain extension amine (28.53gSPA+161.65gDMAC) after 190.2g, after stirring 5min, resulting polymers is transferred and enter curing
Kettle (D-FETK).Stirring is opened, is added into D-FETK and grinds uniform pulp solution in advance, reaction curing 9h obtains polymer
Stoste.
Dry spinning: transfer polymer dope to spinning box (SPTK), vacuum defoamation stoste 3h obtains spinning solution.To spinning
Silk stock solution carries out dry spinning, and upper river in Zhejiang Province temperature is set as 258 DEG C, and lower river in Zhejiang Province temperature is set as 194 DEG C, spinning rate 800m/min,
40 denier of silk oil-containing denier, obtains final polyurethane elastomeric fiber.Each material proportion relationship is as shown in 1 data of table:
Each substance of table 1 matches tables of data
Wherein: A is RA2 institute polymer, polymer solid content, i.e. A is the quality summation of following substance:
A=mPTMEG+mMDI+mUE+mUA+mST+mSPA
The preparation of embodiment 1-3 laboratory sample
When preparing embodiment 1-3 sample, Examination on experimental operation is identical as preparation comparative sample operating method, the difference is that
When preparation emulsifies pulp solution, a certain amount of iron oxide magnetic powder (γ-Fe2O3), the adding proportion of magnetic powder such as following table joined
It is shown:
Tables of data is added in 2 laboratory sample 1-3 magnetism agent of table
Wherein: A is RA2 institute polymer, polymer solid content, i.e. A is the quality summation of following substance:
A=mPTMEG+mMDI+mUE+mUA+mCEPPA+mST+mSPA
Each embodiment polyurethane elastomeric fiber physical index is listed in Table 4 below:
Each embodiment polyurethane elastomeric fiber physical index of table 3
It can be seen that from 3 physical index of table and select the formula of embodiment 2 magnetic to polyurethane elastomeric fiber progress modified, it is fine
Dimension magnetism significantly improves, and polymer good spinning property, meets industrialization production requirement；Obtained elastomer mechanical property and
Elastic property can satisfy and take and household items use, have higher economic value without obvious damage.
Claims (10)
1. a kind of preparation method of magnetic polyurethane elastomer, it is characterized in that this method prepares magnetic powder dispersion by grinding emulsification
Magnetic polyurethane spinning solution is made in pulp solution incorporation polyether polyols by uniform magnetic slurry solution, then should
Spinning solution is prepared into final magnetic polyurethane elastomer using dry spinning；Wherein: polyether polyols are by polyethers two
Alcohol, diisocyanate ester condensation addition polymerization form performed polymer, then the performed polymer, diamine, the common chain extension of chain terminating agent are formed.
2. the preparation method of a kind of magnetic polyurethane elastomer according to claim 1, it is characterized in that the magnetic powder is
Iron oxide magnetic powder γ-Fe2O3, the modified iron oxide magnetic powder of the method through overdoping, absorption, infiltration, cladding, chromium dioxide magnetic powder
CrO2, metal magnetic and barium ferrite magnetic powder, magnetic powder size controlling account for magnetic polyurethane elastomer in < 1um, the magnetic powder
Weight ratio be 2%-10%, few fibers magnetize magnetic to assign fiber.
3. the preparation method of a kind of magnetic polyurethane elastomer according to claim 1, it is characterized in that the solvent is
N,N-Dimethylformamide DMF, n,N-dimethylacetamide DMAC or N, the amides homologue of N- diethylformamide DEF.
4. the preparation method of a kind of magnetic polyurethane elastomer according to claim 1, it is characterized in that institute
Stating magnetic slurry solution is that magnetic powder and polyether polyols and auxiliary material are made by grinder grinding emulsification, the auxiliary material
Including antioxidant, color inhibition agent, lubricant, ultraviolet absorbing agent.
5. the preparation method of a kind of magnetic polyurethane elastomer according to claim 1, it is characterized in that institute
Stating polyetherdiol is polytetrahydrofuran diol, polyoxygenated olefin diols or copolyether glycol, and polyetherdiol has 1000-
5000 molecular weight.
6. the preparation method of a kind of magnetic polyurethane elastomer according to claim 1, it is characterized in that two isocyanide
Acid esters is methyl diphenylene diisocyanate MDI, toluene di-isocyanate(TDI) TDI, naphthalene diisocyanate NDI, hexa-methylene two are different
Cyanate HDI, poly methylene poly phenyl poly isocyanate PAPI or 4,4, one dicyclohexyl methyl hydride diisocyanate HMDI；Institute
It states in performed polymer, diisocyanate end moieties mass percent accounts for the 1.6-3.0% of performed polymer.
7. the preparation method of a kind of magnetic polyurethane elastomer according to claim 1, it is characterized in that the diamine
For ethylenediamine UE, propane diamine UA, 1- methyl-1,5- pentanediamine SPA, hexamethylene diamine or p-phenylenediamine；The chain terminating agent includes two
Ethamine ST, n-butanol UB.
8. the preparation method of a kind of magnetic polyurethane elastomer according to claim 1, it is characterized in that the polyurethane
In polymer, (dihydric alcohol terminal hydroxy group molal quantity++ 1/2 chain terminating agent molal quantity of diamine Amino End Group molal quantity)/isocyanate group
Group molal quantity=1.01-1.05；When chain extension, binary amine end groups molal quantity/chain terminating agent end group molal quantity=12.5-21.0.
9. the preparation method of a kind of magnetic polyurethane elastomer according to claim 1, it is characterized in that described magnetic poly-
Urethane spinning solution has the number-average molecular weight of 40000-500000.
10. the preparation method of a kind of magnetic polyurethane elastomer according to claim 1, it is characterized in that described magnetic poly-
Urethane spinning solution mass concentration is 30-45%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112813519A (en) * | 2020-12-31 | 2021-05-18 | 河北艾科瑞纤维有限公司 | Preparation method of magnetic acrylic fiber and magnetic acrylic fiber |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101294594B1 (en) * | 2011-09-20 | 2013-08-16 | 한국과학기술연구원 | Nanofiber with magnetic property and its preparation method |
| CN103643345A (en) * | 2013-12-18 | 2014-03-19 | 浙江华峰氨纶股份有限公司 | Preparation method of urethane elastic fiber with function of resisting electromagnetic radiation |
| CN104592477A (en) * | 2015-02-16 | 2015-05-06 | 中北大学 | Preparation method of high-performance magnetic polyurethane elastomer composites |
| CN106319671A (en) * | 2016-10-25 | 2017-01-11 | 福建星宏新材料科技有限公司 | Functional textile fiber capable of improving biological electromagnetic field of human body and fabric thereof |
| CN107119340A (en) * | 2017-05-08 | 2017-09-01 | 南通蛇类治疗研究所 | The both effectiveness health clothing of element fabric |
-
2019
- 2019-01-30 CN CN201910093057.3A patent/CN109943907B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101294594B1 (en) * | 2011-09-20 | 2013-08-16 | 한국과학기술연구원 | Nanofiber with magnetic property and its preparation method |
| CN103643345A (en) * | 2013-12-18 | 2014-03-19 | 浙江华峰氨纶股份有限公司 | Preparation method of urethane elastic fiber with function of resisting electromagnetic radiation |
| CN104592477A (en) * | 2015-02-16 | 2015-05-06 | 中北大学 | Preparation method of high-performance magnetic polyurethane elastomer composites |
| CN106319671A (en) * | 2016-10-25 | 2017-01-11 | 福建星宏新材料科技有限公司 | Functional textile fiber capable of improving biological electromagnetic field of human body and fabric thereof |
| CN107119340A (en) * | 2017-05-08 | 2017-09-01 | 南通蛇类治疗研究所 | The both effectiveness health clothing of element fabric |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112813519A (en) * | 2020-12-31 | 2021-05-18 | 河北艾科瑞纤维有限公司 | Preparation method of magnetic acrylic fiber and magnetic acrylic fiber |
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