CN100540761C - The preparation method of a kind of PTMEG modification sodium-based montmorillonite and heat-resisting polyurethane elastomeric fiber - Google Patents
The preparation method of a kind of PTMEG modification sodium-based montmorillonite and heat-resisting polyurethane elastomeric fiber Download PDFInfo
- Publication number
- CN100540761C CN100540761C CNB2005100733978A CN200510073397A CN100540761C CN 100540761 C CN100540761 C CN 100540761C CN B2005100733978 A CNB2005100733978 A CN B2005100733978A CN 200510073397 A CN200510073397 A CN 200510073397A CN 100540761 C CN100540761 C CN 100540761C
- Authority
- CN
- China
- Prior art keywords
- preparation
- ptmeg
- heat
- solution
- prepolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Artificial Filaments (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a kind of with polyether polyol (PTMEG) modified montmorillonoid, with the imvite-polyether polyol of modification as the flexible polyurethane segment, preparation montmorillonite/polyurethane nano composite polymer (PU/MMT) improves the heat resistance of polyurethane elastomeric fiber and the method for mechanical property.Wherein imvite is a sodium-based montmorillonite, and sodium-based montmorillonite is behind the polyether polyol intercalation modifying first time, and the cheating engaging layer spacing is increased for the first time; Utilize isocyanates to its intercalation modifying for the second time in dicyandiamide solution, the cheating engaging layer spacing is increased for the second time; The prepolymer of intercalation modifying again with the polymerization of small molecule amine chain extension, the cheating engaging layer spacing is increased for the third time, finally makes exfoliated montmorillonite/polyurethane nano-complex, thereby improves resistant polyurethane hot property and mechanical property.
Description
Technical field
The present invention relates to a kind of modified by polyether glycol imvite that utilizes, then with modified montmorillonoid as part soft chain segment synthesis of polyurethane polymer, to improve the method for its heat resistance and mechanical property.
Background technology
Spandex fibre has the intensity height at normal temperatures, light specific gravity, plurality of advantages such as good high elasticity and elastic recovery rate.But the spandex stainability is poor, when spandex and the dyeing of other fiber blends, when particularly washing the ammonia blending, influenced by the spandex heat resistance, washs the ammonia BLENDED FABRIC and is difficult to satisfy the diversified color requirement of people.
Therefore, in recent years successively the someone be engaged in the research of high temperature resistant spandex.U.S. Pat 5879799 reports use 2 of various mol ratios, 4-MDI and 4, and the compound isocyanates of 4-MDI improves the spandex heat resistance; Japan Patent (JP7-82608, JP08-020625, JP08-176253, JP08-176268) also report adopts identical method to develop high temperature resistant spandex.Behind United States Patent (USP) (US6203901) the report nano imvite material modification, add in the polyether polyols with reduced unsaturation, can improve the performance of polyurethane elastomeric fiber (being the spandex silk) in dyeing and finishing process.Chinese patent 03153706 is set forth the method that a kind of laminar nano compound strengthens spandex silk intensity.
Summary of the invention
The object of the present invention is to provide a kind of modified by polyether glycol imvite that utilizes, then with modified montmorillonoid as part soft chain segment synthesis of polyurethane polymer, to improve the method that its heat resistance improves mechanical property simultaneously.
Another object of the present invention is to provide a kind of heat resistance and all good polyurethane fibers of producing with said method of mechanical property.
A further object of the present invention is to provide a kind of preparation method who can be used for the modified by polyether glycol imvite among the above-mentioned preparation method.
The preparation method of heat-resisting polyurethane elastomeric fiber of the present invention may further comprise the steps:
Sodium-based montmorillonite is used the softex kw modification earlier, with PTMEG it is carried out the intercalation modifying first time again, obtain PTMEG modification sodium-based montmorillonite of the present invention;
With isocyanates and polyether polyol according to mol ratio 1.5-2.0 mix, the step of reaction prepolymer;
In the prepolymer that prepolymerization step generates, remaining isocyanate solution, add the step that solvent orange 2 A dissolves prepolymer, isocyanates;
The modified by polyether glycol imvite that is dissolved in solvent orange 2 A is added in the above-mentioned isocyanate solution with 0.1～5% of polyurethane mass content, carried out the intercalation modifying second time;
Intercalation modifying imvite for the second time and prepolymer system mix, with the linear aliphatic family amine aqueous solution of carbon number 2-16 as chain extender, add in the above-mentioned prepolymer, carry out chain extending reaction, make the cheating engaging layer spacing increase for the third time, and finally peel off, apparent viscosity 1000～10000 pools when generating 20 ℃, fusing point is smaller or equal to the step of 200 ℃ montmorillonite/polyurethane composition;
Above-mentioned polyurethane is made the step of the heat-resisting polyurethane fiber of described elasticity with dry spinning.
Described modified montmorillonoid is the modified by polyether glycol sodium-based montmorillonite, and the structure of polyether polyol is HO-[(CH
2)
4-O]
n-H, wherein n is the integer of 20-28, the integer of preferred 25-28.
The prepolymerization reaction temperature is more than 65 ℃, and overall process is at N
2Carry out in the atmosphere, the generation prepolymer is a carbamate, and its structure is R
1-NH-COO-R
2, wherein, R
1, R
2Be alkyl.
The time of intercalation is 2～4 hours for the second time, and temperature is 60～80 ℃, carries out in nitrogen atmosphere.
The time of chain extending reaction is 30～90 minutes, and initial temperature is 5～10 ℃, carries out in nitrogen atmosphere.
Described isocyanates be its contained isocyanate groups with PTMEG in hydroxyl reaction active identical 4,4 '-methyl diphenylene diisocyanate (MDI) or 1, the 6-hexamethylene diisocyanate, its general structure is OCN-R-NCO, wherein R is the saturated alkane base, preferred isocyanate is 4,4 '-methyl diphenylene diisocyanate (MDI), and the mol ratio of MDI and PTMEG is 1.5-2.0.
Described prepolymer is the prepolymers of two ends by the isocyanate groups sealing.
Solvent orange 2 A is dimethylacetylamide (DMAc) or dimethyl formamide (DMF).
Adding solvent orange 2 A in the prepolymer that generates, with the dissolving prepolymer, its polymer quality content is 20-40%, preferred 25-35%.
The modified montmorillonoid mass content is 5-10% in the solution that modified by polyether glycol sodium-based montmorillonite and solvent orange 2 A form, it is added in the pre-polymer solution, reaction, its imvite content is the 0.1-5% of polyether polyols with reduced unsaturation, replenish an amount of solvent and make that polymer quality is 50% of a solvent quality, then with micromolecule linear aliphatic family amine to its further chain extension.
Chain extender linear aliphatic family amine as chain extending reaction is ethylenediamine, propane diamine, pentanediamine, hexamethylene diamine, lauryl amine, diethylamine, di-n-butylamine or their combination, and the general structure of monoamine is NH
2-R
3, the general structure of diamine is NH
2-R
4-NH
2, wherein, R
3, R
4Be the saturated alkane base, preferred ethylenediamine, propane diamine, diethylamine or their combination.
Make apparent viscosity preferred 3000-8000 pool in the time of 20 ℃ of polyurethane.
With the dry spinning method, the line density of spinning is 40 denier polyurethane elastomers, and wherein, spinning speed is 500 meters/minute.
The preparation method of PTMEG modification sodium-based montmorillonite of the present invention comprises:
Sodium-based montmorillonite is dissolved in the deionized water, and the quality of imvite is 5～10% of a deionized water quality, stir and filter insoluble matter with 300 mesh filter screens, solution B;
In solution B, add softex kw, addition is 25～35% of an imvite quality, add deionized water, make the gross mass of imvite and softex kw 5～10% of the ionized water gross mass that accounts for, stirring reaction is 2～6 hours under 60～80 ℃ of conditions, leave standstill aquation 24～48 hours, and got solution C;
PTMEG is dissolved in the middle of the solvent orange 2 A, the quality of PTMEG be in the solution C solid masses 10～30%, the quality of solvent orange 2 A is equal to or greater than the quality of solution C, the solvent orange 2 A solution of solution C and PTMEG is mixed, high-speed stirred is 2～8 hours under 60～85 ℃ of conditions, continue to be heated to the detection moisture and be lower than 0.1%, get modified montmorillonoid D;
With modified montmorillonoid D drying, grind, with the screening of 300 mesh filter screens, promptly obtain polyglycols modified montmorillonoid of the present invention, the cheating engaging layer spacing is increased for the first time.
Through the imvite of PTMEG modification in solvent orange 2 A, with isocyanates 4,4 '-methyl diphenylene diisocyanate (MDI) carries out modification to it, make the intercalation increase for the second time of cheating engaging layer spacing, the MDI addition is 2～5% of a PTMEG modified montmorillonoid quality, the solvent orange 2 A addition makes the gross mass of MDI and modified montmorillonoid account for 5～10% of solvent orange 2 A quality, obtains solution E, and solution E stirred 2-4 hour under 60～80 ℃ of conditions.
Used imvite is a natural sodium-based montmorillonite or by the sodium-based montmorillonite that obtains behind the calcium-base montmorillonite sodium modification.
The present invention utilizes the more rich imvite of domestic mineral reserve, in organic solvent system, with the PTMEG modification, big molecule is entered between cheating engaging layer, and its interlamellar spacing is increased for the first time; Then modified montmorillonoid is carried out the intercalation prepolymerization as part soft chain segment and isocyanates, the interlamellar spacing of imvite is increased for the second time; The prepolymer of intercalation modifying again with the polymerization of small molecule amine chain extension, the cheating engaging layer spacing is increased for the third time, finally makes the montmorillonite/polyurethane nano-complex, thereby improves the heat resistance and the mechanical property of polyurethane elastomeric fiber.And necessarily to spin the spandex product that speed obtained for 40 dawn.The content of mentioning among the present invention except that specifying, is the quality percentage composition.
The specific embodiment
Technical scheme of the present invention describes in detail by following embodiment, and the heat-resisting spandex silk properties of product that obtain from each embodiment are attached.From table 1 data as can be seen, the extension at break of heat-resisting spandex silk and fracture strength improve a lot than common spandex.From table 2 data as can be seen, under identical thermal weight loss (TGA) analysis condition, the weightless temperature of heat-resisting spandex silk has raising about 10 ℃ than common spandex silk.The spandex silk that proof contains the polyether montmorillonite soft chain segment has heat resistance really.
Embodiment 1
The sodium-based montmorillonite that takes by weighing the 30g drying is dissolved in the 350g deionized water, 40 ℃ stir into stable homogeneous system after, filter insoluble suspended matter with 300 mesh filter screens and obtain homogeneous solution B;
The 10g softex kw is dissolved in the 150g deionized water, and in the middle of the solution B that the back adding above-mentioned steps that stirs obtains, 70 ℃ were stirred 3 hours, and obtained solution C;
Take by weighing 8g PolyTHF (PTMEG) and be dissolved among the 600g DMAc, stir under 50 ℃, add in the solution C that step 2 obtains, 70 ℃ continue stirring until water content and are lower than 0.07%, obtain solution D, are reflected at N
2Carry out in the environment;
With the solution D drying, remove solvent, and the modified montmorillonoid that obtains is ground, sieved final vacuum dry 12 hours with 300 mesh filter screens, standby;
Accurately take by weighing the modified montmorillonoid 3.5g that step 4 obtains and be dissolved in the middle of the 42.5g DMAc, and in solution, add isocyanates MDI 0.2g,, obtain modified solution E, be reflected at N in 75 ℃ of stirring reactions 4 hours
2Carry out in the environment;
Making MDI 42.50g and number-average molecular weight is that 2000 PTMEG 200g carries out prepolymerization reaction, adds 480.0g DMAc and makes above-mentioned prepolymer dissolving evenly;
Keep unreacted isocyanate groups, stir after adding the solution E that step 5 obtains, and keep 70 ℃ and stop 20min it is fully mixed;
Be dissolved among the 75g DMAc with ethylenediamine 2.70g, diethylamine 0.45g, propane diamine 0.80g, be added drop-wise to and carry out chain extending reaction in the above-mentioned system;
Finally obtain the polymer of apparent viscosity about 5000P (20 ℃).After this polymer deposited 48h, obtain the spandex silk with dry spinning.
Embodiment 2
The sodium-based montmorillonite that takes by weighing the 30g drying is dissolved in the 350g deionized water, 40 ℃ stir into stable homogeneous system after, filter insoluble suspended matter with 300 mesh filter screens and obtain homogeneous solution B;
The 15g softex kw is dissolved in the 150g deionized water, and in the middle of the solution B that the back adding above-mentioned steps that stirs obtains, 70 ℃ were stirred 2 hours, and obtained solution C;
Take by weighing 8g PolyTHF (PTMEG) and be dissolved among the 600g DMAc, stir under 50 ℃, add in the solution C that step 2 obtains, 70 ℃ continue stirring until water content and are lower than 0.07%, obtain solution D, are reflected at N
2Carry out in the environment;
With the solution D drying, remove solvent, and the modified montmorillonoid that obtains is ground, sieved final vacuum dry 12 hours with 300 mesh filter screens, standby;
Accurately take by weighing the modified montmorillonoid 3.5g that step 4 obtains and be dissolved in the middle of the 42.5g DMAc, and in solution, add isocyanates MDI 0.5g,, obtain modified solution E, be reflected at N in 75 ℃ of stirring reactions 3 hours
2Carry out in the environment;
Making MDI 37.50g and number-average molecular weight is that 2000 PTMEG 200g carries out prepolymerization reaction, adds 465.0g DMAc and makes above-mentioned prepolymer dissolving evenly;
Keep unreacted isocyanate groups, stir after adding the solution E that step 5 obtains, and keep 70 ℃ and stop 20min it is fully mixed;
Be dissolved among the 83g DMAc with ethylenediamine 2.29g, diethylamine 0.39g, propane diamine 0.71g, be added drop-wise to and carry out chain extending reaction in the above-mentioned system;
Finally obtain the polymer of apparent viscosity about 5000P (20 ℃).After this polymer deposited 48h, obtain the spandex silk with dry spinning.
Attached:
Heat-resisting spandex silk performance such as following table 1 and table 2.
The mechanical property of heat-resisting spandex silk of table 1 and common spandex silk is (spinning fast 500m/min, 40 dawn) relatively
The heat resistance of heat-resisting spandex silk of table 2 and common spandex silk is (NETZSCHTG209F1,10 ℃ of speed/min) relatively
Claims (17)
1, a kind of preparation method of PTMEG modification sodium-based montmorillonite is characterized in that: comprising:
Sodium-based montmorillonite is dissolved in the deionized water, and the quality of imvite is 5～10% of a deionized water quality, stir and filter insoluble matter with 300 mesh filter screens, solution B;
In solution B, add softex kw, addition is 25～35% of an imvite quality, add deionized water, make the gross mass of imvite and softex kw 5～10% of the ionized water gross mass that accounts for, stirring reaction is 2～6 hours under 60～80 ℃ of conditions, leave standstill aquation 24～48 hours, and got solution C;
PTMEG is dissolved in the middle of solvent orange 2 A dimethylacetylamide or the dimethyl formamide, the quality of PTMEG be in the solution C solid masses 10～30%, the quality of solvent orange 2 A is equal to or greater than the quality of solution C, the A solution of solution C and PTMEG is mixed, high-speed stirred is 2～8 hours under 60～85 ℃ of conditions, continue to be heated to the detection moisture and be lower than 0.1%, get modified montmorillonoid D;
With the D drying, grind, with the screening of 300 mesh filter screens, promptly obtain PTMEG modification sodium-based montmorillonite of the present invention, the cheating engaging layer spacing is increased for the first time.
2, the preparation method of a kind of PTMEG modification sodium-based montmorillonite according to claim 1 is characterized in that: described imvite is natural sodium-based montmorillonite or the sodium-based montmorillonite that obtained behind sodium modification by calcium-base montmorillonite.
3, the preparation method of a kind of PTMEG modification sodium-based montmorillonite according to claim 1, it is characterized in that: through the imvite of PTMEG modification in solvent orange 2 A, with isocyanates 4,4 '-diphenyl methyl alkane vulcabond carries out modification to it, makes the cheating engaging layer spacing through the intercalation increase second time.
4, the preparation method of a kind of PTMEG modification sodium-based montmorillonite according to claim 3, it is characterized in that: 4, the addition of 4 '-diphenyl methyl alkane vulcabond is 2～5% of a PTMEG modified montmorillonoid quality, the solvent orange 2 A addition makes 4,4 '-diphenyl methyl alkane vulcabond and account for 5～10% of solvent orange 2 A quality through the gross mass of the imvite of PTMEG modification obtains solution E.
5, the preparation method of a kind of PTMEG modification sodium-based montmorillonite according to claim 4 is characterized in that: described solution E stirred 2～4 hours under 60～80 ℃ of conditions.
6, a kind of preparation method of heat-resisting polyurethane elastomeric fiber is characterized in that: order comprises the steps:
Preparation method according to claim 1, preparation modification sodium-based montmorillonite, wherein modified montmorillonoid is the modified by polyether glycol imvite, the structural formula of described polyether polyol is HO-[(CH
2)
4-O]
n-H, wherein n is the integer of 20-28;
Isocyanates is mixed the step of reaction prepolymer according to mol ratio 1.5～2.0 with polyether polyol;
Add the step that solvent orange 2 A makes prepolymer and isocyanates dissolving in prepolymer that prepolymerization step generates and remaining isocyanates, described solvent orange 2 A is dimethylacetylamide or dimethyl formamide;
The PTMEG modified montmorillonoid is dissolved in solvent orange 2 A, and adds to 0.1～5% of polyurethane mass content in the solution of above-mentioned prepolymer, isocyanates, carry out the intercalation modifying second time;
Intercalation modifying imvite for the second time and prepolymer system mix, with the linear aliphatic family amine aqueous solution of carbon number 2～16 as chain extender, add in the above-mentioned prepolymer, carry out chain extending reaction, make the cheating engaging layer spacing increase for the third time, and finally peel off, apparent viscosity 1000～10000 pools when generating 20 ℃, fusing point is smaller or equal to the step of 200 ℃ montmorillonite/polyurethane composition;
Above-mentioned polyurethane is made the step of the heat-resisting polyurethane fiber of described elasticity with dry spinning.
7, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 6 is characterized in that: modification is 25～28 integer with n in the structural formula of polyether polyol.
8, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 6 is characterized in that: the temperature of prepolymerization reaction is more than 65 ℃, and overall process is carried out in nitrogen atmosphere, and the prepolymer of generation is a carbamate, and its structure is R
1-NH-COO-R
2, wherein, R
1, R
2Be alkyl.
9, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 6 is characterized in that: the time of intercalation is 2～4 hours for the second time, and temperature is 60～80 ℃, carries out in nitrogen atmosphere.
10, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 6 is characterized in that: the time of chain extending reaction is 30～90 minutes, and initial temperature is 5～10 ℃, carries out in nitrogen atmosphere.
11, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 6 is characterized in that: described isocyanates is 1, the 6-hexamethylene diisocyanate.
12, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 6 is characterized in that: adding solvent orange 2 A in generating prepolymer, with the dissolving prepolymer, its polymer quality content is 20～40%.
13, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 12 is characterized in that: adding solvent orange 2 A in generating prepolymer, with the dissolving prepolymer, its polymer quality content is 25～35%.
14, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 6 is characterized in that: the modified montmorillonoid mass content is 5～10% in the solution that PTMEG modification sodium-based montmorillonite and solvent orange 2 A form.
15, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 6 is characterized in that: as the linear aliphatic family amine of the chain extender of chain extending reaction is a kind of in ethylenediamine, propane diamine, pentanediamine, hexamethylene diamine, lauryl amine, diethylamine, the di-n-butylamine or their combination.
16, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 15 is characterized in that: as the linear aliphatic family amine of the chain extender of chain extending reaction is a kind of in ethylenediamine, propane diamine, the diethylamine or their combination.
17, the preparation method of a kind of heat-resisting polyurethane elastomeric fiber according to claim 6 is characterized in that: the apparent viscosity that makes polyurethane is the 3000-8000 pool in the time of 20 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100733978A CN100540761C (en) | 2005-06-03 | 2005-06-03 | The preparation method of a kind of PTMEG modification sodium-based montmorillonite and heat-resisting polyurethane elastomeric fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100733978A CN100540761C (en) | 2005-06-03 | 2005-06-03 | The preparation method of a kind of PTMEG modification sodium-based montmorillonite and heat-resisting polyurethane elastomeric fiber |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1693549A CN1693549A (en) | 2005-11-09 |
| CN100540761C true CN100540761C (en) | 2009-09-16 |
Family
ID=35352665
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100733978A Expired - Fee Related CN100540761C (en) | 2005-06-03 | 2005-06-03 | The preparation method of a kind of PTMEG modification sodium-based montmorillonite and heat-resisting polyurethane elastomeric fiber |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100540761C (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383182C (en) * | 2005-11-15 | 2008-04-23 | 中国科学院广州化学研究所 | Organic montmorillonite and its composite with polyurethane |
| CN100491433C (en) * | 2006-06-13 | 2009-05-27 | 中国工程物理研究院化工材料研究所 | Polyurethane microporous elastomer composite material and preparation method thereof |
| CN101407947B (en) * | 2008-11-21 | 2012-05-09 | 东华大学 | Montmorillonite / polypropylene / polylactic acid composite fiber material and preparing method thereof |
| CN106279617A (en) * | 2016-08-23 | 2017-01-04 | 武汉科利尔新材料有限公司 | A kind of polyurethane cladding two dimension peels off the preparation method of activated montmorillonite |
| CN111019100B (en) * | 2018-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Montmorillonite-modified barrier polyester and preparation method thereof |
| CN112979905B (en) * | 2019-12-13 | 2023-03-14 | 江苏苏博特新材料股份有限公司 | Block polyurethane polymer, polymer modified bentonite admixture thereof, and preparation and application thereof |
| TWI772203B (en) | 2021-10-15 | 2022-07-21 | 南亞塑膠工業股份有限公司 | Thermoplastic polyurethane resin suitable for melt spinning |
-
2005
- 2005-06-03 CN CNB2005100733978A patent/CN100540761C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1693549A (en) | 2005-11-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100540761C (en) | The preparation method of a kind of PTMEG modification sodium-based montmorillonite and heat-resisting polyurethane elastomeric fiber | |
| CN107698729B (en) | Medium-soft polyurethane surface layer resin and preparation method thereof | |
| CN101096779A (en) | Process for producing polyether type easy dyeing spandex fiber | |
| CN103483539B (en) | Poly-(carbonic ether-ether) type aqueous polyurethane, water-based polyurethane adhesive and preparation method thereof | |
| CN102220653B (en) | Preparation method of heat resistant spandex fiber | |
| CN102719928B (en) | Preparation method for high-stress high-resilience polyurethane fiber | |
| CN102702471A (en) | Method for preparing solvent-free aqueous polyurethane dispersion | |
| CN102154729B (en) | Preparation method of high-elongation and high-draft polyurethane fibers | |
| CN103757741B (en) | A kind of preparation method with the spandex fibre of high resilience energy | |
| CN105837780B (en) | A kind of easy coloring polyurethane elastomeric fiber and preparation method thereof | |
| CN100472003C (en) | Quaternary ammonium salt montmorillonite modified polyurethane heat resistant elastic fibre and its preparation method | |
| CN1301280C (en) | Polyurethane urea elastic fiber having high heat resistance and fine shape-setting and process for preparing same | |
| CN103898631B (en) | Rubber combined elastomer of a kind of polyurethane-urea and preparation method thereof | |
| CN109322008B (en) | Method for improving performance stability of spandex product | |
| CN100471887C (en) | Heat-resisant elastic fiber polyurethane modified by diamine montmorillonite and preparation method | |
| CN102070769A (en) | Pyridine quaternary ammonium salt polyurethane and preparation method thereof | |
| CN106381561A (en) | Spandex fiber, preparation method of spandex fiber, and fabric | |
| CN101096783A (en) | Process for manufacturing chlorine-resistant spandex fibre | |
| CN106758387A (en) | A kind of environmentally friendly formaldehydeless chlorine-resistant cotton color fixing agent | |
| CN105506777A (en) | Polyurethane elastic fiber easy to adhere and preparation method thereof | |
| US20220033997A1 (en) | Polyurethane elastic fiber with flame retardant function and preparation method thereof | |
| CN107663671A (en) | A kind of thermal polyurethane elastomer and preparation method thereof | |
| CN102534856B (en) | Preparation method of spandex spinning stock solution by PCL dry method | |
| KR20110079377A (en) | Producing method of polyurethanure elastic fiber having improved dying property | |
| CN101654503A (en) | Method for synthesizing high heat-resistance linear polyurethane resin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20090220 Address after: 365, South Binjiang Road, petrochemical District, Taicang Port Development Zone, Jiangsu, China: 215433 Applicant after: Sinochem International (Suzhou) new material research & Development Co., Ltd. Address before: The 10 floor, Tokai Hotel, No. 15, Linping West Street, Yuhang District, Zhejiang, Hangzhou Province, China: 311100 Applicant before: Zhonghua International Yu Hang High Molecular Material Research, Development and |
|
| ASS | Succession or assignment of patent right |
Owner name: CENTRALIZATION INTERNATIONAL ( SUZHOU ) NEW MATERI Free format text: FORMER OWNER: CENTRALIZATION INTERNATIONAL YUHANG MACROMOLECULE MATERIALS RESEARCH AND DEVELOPMENT DESIGN CO., LTD. Effective date: 20090220 |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Sinochem Modern Environmental Protection Chemicals (Xi'an) Co., Ltd. Assignor: Sinochem International (Suzhou) New Material R&D Co., Ltd. Contract record no.: 2011610000137 Denomination of invention: PTMEG modified Na-montmorillonite and heat resistant polyurethane elastic fibre preparation method Granted publication date: 20090916 License type: Exclusive License Open date: 20051109 Record date: 20110725 |
|
| ASS | Succession or assignment of patent right |
Owner name: TAICANG ZHONGHUA ENVIRONMENTAL PROTECTION MEDICAL Free format text: FORMER OWNER: ZHONGHUA INTERNATIONAL (SUZHOU) NEW MATERIAL R + D CO., LTD. Effective date: 20120301 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20120301 Address after: 215433 No. 18 South Binjiang Road, petrochemical District, Taicang Port Development Zone, Jiangsu, China Patentee after: Sinochem Taicang Environmental Protection Chemical Co., Ltd. Address before: 215433 No. 365 South Binjiang Road, petrochemical District, Taicang Port Development Zone, Jiangsu, China Patentee before: Sinochem International (Suzhou) New Material R&D Co., Ltd. |
|
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090916 Termination date: 20160603 |