CN1304944A - Polyether/polyester type polyurethane material and process for preparing condom from it - Google Patents
Polyether/polyester type polyurethane material and process for preparing condom from it Download PDFInfo
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- CN1304944A CN1304944A CN 00109920 CN00109920A CN1304944A CN 1304944 A CN1304944 A CN 1304944A CN 00109920 CN00109920 CN 00109920 CN 00109920 A CN00109920 A CN 00109920A CN 1304944 A CN1304944 A CN 1304944A
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Abstract
A process for preparing polyether/polyester-type polyurethane features the two-step polymerization of diisocyanate, polyether polyol, polyester polyol, chain-enlarging agent, lubricant and antioxidant. The condom is prepared through dissolving obtained polyurethane is mixed solvent, dipping the condom core die in it, drying and demoulding. Its advantages are simple process, short period, thin and comfortable products, no toxicity, high strength and flexibility and high thermal conductivity.
Description
The invention belongs to the manufacturing technology field of polyurethane material and goods thereof, the method that is specifically related to a kind of preparation method of polyether/polyester type polyurethane material and utilizes this material to adopt dip forming to make condom.
Traditional condom is made material owing to be natural emulsion, thereby its product ubiquity and use not very comfortablely, easily causes allergy, and rupture rate is high and can not shield problems such as fraud hiv virus and storage period be short fully.For this reason, people begin to do one's utmost to seek novel material and substitute natural emulsion and make condom from the synthetic materials field.According to present disclosed technology, alternative natural emulsion is made condom and has more that the material of excellent properties is mainly polyurethane termoplastic elastomer, " polyesterurethane condom " that discloses as CN1142838A.Though the disclosed this urethane of this technical scheme has the more unexistent excellent properties of natural emulsion, but its elasticity and flexibility should seem inadequately as the material of making condom, though next condom that provides supports molded method can be than prior art (U.S4,576,156 and US4,684,490 etc.) can produce the thin soft and whippy condom of low modulus, wall fast, but complex manufacturing process, cycle are long, required processing units is also comparatively complicated, accuracy requirement is high, the control condition harshness.
An object of the present invention is to overcome the defective that prior art exists, intend providing the preparation method of a kind of elasticity and the better polyether/polyester type polyurethane material of flexibility.
Another object of the present invention then is in order to solve in the prior art the relevant problem that exists in the condom of making, and provides that a kind of making processes is simple, the cycle short, the preparation method of easy and simple to handle, polyurethane condom that product quality is high.
An object of the present invention is to be reached by a kind of like this technical solution: this technical solution is to contain in the prior art prescription on the basis of vulcabond, polyester polyol, chainextender, lubricant and oxidation inhibitor, also be added with polyether glycol, and the ratio range of each component following (weight percent):
Vulcabond 19～27%
Polyether glycol 23～45%
Polyester polyol 24～48%
Chainextender 1～8%
Lubricant 1～5%
During oxidation inhibitor 1～5% preparation, adding polyether glycol, polyester polyol mix under 50～80 ℃ earlier; Add vulcabond again, 60～90 ℃ of following prepolymerization reactions 30～50 minutes; And then add chainextender, lubricant, oxidation inhibitor and put into screw extrusion press after mixing, extrude after 2～5 minutes 100～210 ℃ of following polyreactions, and cooling, pelletizing, drying.
Wherein vulcabond be except that can selecting diphenylmethanediisocyanate (MDI), isophorone diisocyanate (IPDI), xylylene diisocyanate (XDI), cyclohexyl diisocyanate for use, also can select in tolylene diisocyanate (TDI), ethylbenzene vulcabond (EDI), six methylene diisocyanates (HDI) any for use.
Polyester polyol also can be selected in polyethylene glycol adipate, poly-adipate glycol propylene glycol ester, the poly-adipate glycol butanediol ester any for use except that can selecting the poly-epsilon-caprolactone glycol for use, molecular weight control is 1000～2000.
Polyether glycol can be selected any in polypropylene oxide glycol, polyethylene oxide glycol, polyoxyethylene oxypropylene copolyether glycol, the equal polyethers glycol of THF-, the polybutene glycol for use, and molecular weight control is 1000～2000.
The optional spent glycol of chainextender, a condensed ethandiol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,5 pentanediol, two-hydroxyethyl, any in the cyclohexanediol.
Lubricant can be selected any in methyl-silicone oil, hydroxy silicon oil, the oxyethyl group silicone oil for use.
Oxidation inhibitor then can be selected Lrganoxlolo, Tinuvinp (Chiba-Geigr), 2,6,4 oxidation inhibitor, 2,6-di-tert-butyl cresols, antioxidant 300,2, any in the 5-dialkyl group quinhydrones for use.
Another object of the present invention then reaches by a kind of like this technical solution: the forming process flow process of this technical solution is solution preparation → dipping → drying → demoulding, and the processing condition of this each operation of flow process should be controlled to be:
(1) the solution preparation joins the proportioning of polyether/polyester type polyurethane sizing material by 5～10% (weight) in the mixed solvent, constantly stirs at normal temperatures, and is stand-by after making it to dissolve fully and filtering;
(2) dipping will be water clean up, and the standby condom core in dry back immersed in the polyether/polyester type polyurethane solution that configures 30～50 seconds at normal temperatures, took out dry then.Can flood repeatedly as required after the drying.
(3) dry drying between per twice dipping is to carry out under 40～50 ℃ 8～20 minutes, and is following dry 30～50 minutes at 80～110 ℃ after last dipping finishes;
The demoulding got the condom finished product when (4) the dry postcooling of the demoulding was to room temperature.
Wherein used mixed solvent can be selected two or more preparation of appointing in dimethyl formamide, N,N-DIMETHYLACETAMIDE, dioxane, dimethyl sulfoxide (DMSO), the tetrahydrofuran (THF) for use.
The dipping number of times of core can be 1～5 time, and the requirement of concrete visual condom and the concentration of dipping solution are determined.
The advantage that the present invention has has:
1. the method for preparing polyether/polyester type polyurethane material is simple, and processing ease, processing condition gentleness do not have particular requirement to equipment.
2. nontoxic, the intensity of Zhi Bei polyether/polyester type polyurethane material, flexibility and elasticity height, thermal conductivity is good, and also has not transparency.
3. owing to polyethers, polyester when preparing the urethane proprietary material can arbitrarily be allocated, so can produce the goods of different pliabilitys and intensity according to the requirement of the finished product.
4. the making processes of condom is simple, the cycle short, easy to operate, drying does not need high temperature yet, and manufacturing batch is big.
5. the condom of made is compared with the natural emulsion condom, have thinner, more comfortable, nontoxic, intensity is high, thermal conductivity is good, pliable and tough, no special odor, no sensitization, heat-resisting, wet, the UV-light of energy in storage, and barrier disease virus effectively, comprise the propagation of hiv virus, be not subjected to the influence of oil lubricant or topical therapeutic medicine in addition.
Provide the embodiment of the invention below.
Embodiment one:
480 gram polyethylene glycol adipates and the equal polyethers glycol of 230 gram THF-are joined in the reactor, under 50 ℃, mix; Add diphenylmethanediisocyanate 190 grams again, 70 ℃ of following prepolymerization reactions 40 minutes, add ethylene glycol 30 grams, add 2 again, after 6,4 oxidation inhibitor, 50 grams, hydroxy silicon oil 50 grams mix, put into screw extrusion press immediately, polyreaction was extruded in 2 minutes under 110 ℃ of-210 ℃ of zone heating, and cooling, pelletizing, drying promptly obtain the polyether/polyester type polyurethane PP Pipe Compound.Tensile strength of material 41MPa, elongation at break 560%.
Embodiment two:
Poly-adipate glycol propylene glycol ester of 450 grams and the equal polyethers glycol of 250 gram THF-are joined in the reactor, under 65 ℃, mix; Add diphenylmethanediisocyanate 220 grams again, 75 ℃ of following prepolymerization reactions 35 minutes, add 50 grams 1 then, after 4-butyleneglycol, 10 gram antioxidant 300s and 40 gram methyl-silicone oils mix, put into screw extrusion press immediately, polyreaction was extruded in 5 minutes under 100-180 ℃ of zone heating, and cooling, pelletizing, dry.Tensile strength of material 45MPa, elongation at break 620%.
Embodiment three:
The concrete component of present embodiment prescription is except that chainextender is a condensed ethandiol, all the other components and processing condition are identical with embodiment one, so omit and do not state, be the concrete proportioning difference of each component: polyethylene glycol adipate 310 grams, equal polyethers glycol 380 grams of THF-, diphenylmethanediisocyanate 270 grams, a condensed ethandiol 10 grams, 2,6,4 oxidation inhibitor, 20 grams, hydroxy silicon oil 20 grams.Tensile strength of material 41MPa, elongation at break 680%.
Embodiment four:
343 gram polyethylene glycol adipates are joined in the reactor, and after fusion under 50 ℃, gram THF-all the polyethers glycol fully mixes to add 518 again; Add six methylene diisocyanates, 220 grams, 75 ℃ of following prepolymerization reactions 45 minutes; Add 100 grams 1 again, the 6-hexylene glycol is after 30 gram antioxidant 300s and 20 gram oxyethyl group silicone oil mix, put into screw extrusion press, polyreaction was extruded in 3 minutes under 110～180 ℃ of zone heating, and cooling, pelletizing, dry, strength of materials 41MPa, elongation at break 700%.
Embodiment five:
Poly-hexylene glycol ethylene glycol butanediol ester of 240 grams and 450 gram polypropylene oxide glycol are added in the reactor successively, under 70 ℃, dissolve and mix; Added 210 gram tolylene diisocyanate prepolymerization reactions again 50 minutes; Add 1 again, 5-pentanediol 30 grams, 2, after 6-tertiary butyl cresols 40 gram and methyl-silicone oil 30 grams mix, put into screw extrusion press polyreaction under 110～180 ℃ of zone heating and extruded in 4 minutes, and cooling, pelletizing, drying get final product, strength of materials 40MPa, elongation at break 680%.
Embodiment six:
To gather adipate glycol propylene glycol ester 350 gram earlier and put in the reactor, and, stir and be cooled to 50 ℃ and add polyethylene oxide propane copolyether glycol 350 grams again and mix at 60 ℃ down after the fusion; Add isophorone diisocyanate 190 grams, 80 ℃ of following prepolymerization reactions 35 minutes; Add the two hydroxyethyls of 70 grams again, after 20 gram antioxidant 300s, 20 gram oxyethyl group silicone oil mix, add immediately in the screw extrusion press and extruded in 2 minutes 110～180 ℃ of following zone heating polyreactions, and cooling, pelletizing, dry getting final product, tensile strength of material 42MPa, elongation at break 620%.
Embodiment seven:
Adding the poly-ε of 460 grams earlier---caprolactone diol 70 ℃ of heating fusions down, adds 260 gram polypropylene oxide glycol then and mixes in reactor; Add isophorone diisocyanate 160 gram again, 78 ℃ of following prepolymerization reactions 45 minutes; Add 60 gram hexamethylene ethanol again, after 50 gram 2,5 dioxane quinhydrones and 10 gram hydroxy silicon oils mix, put into screw extrusion press, under 110 ℃～200 ℃ zone heating, mix and extruded in 3 minutes, and cooling, pelletizing, dry getting final product, tensile strength of material 43MPa, extension at break 600%.
Comparative Examples 1:
Add 1000 gram poly adipate succinic acid esters earlier in reactor, 70 ℃ of heating fusions down, add diphenylmethanediisocyanate 250 gram again,, add 1 again 78 ℃ of following prepolymerization reactions 45 minutes, 4-butyleneglycol 45 grams, 2, after 5-dioxane hydrogen ester 50 grams and hydroxy silicon oil 50 grams mix, put into screw extrusion press, extruded in 2 minutes 110 ℃～200 ℃ following zone heating polyreactions, and cooling, pelletizing, dry getting final product.Mechanics of materials intensity 32MPa, elongation at break 500%.
Comparative Examples 2:
With embodiment 1, just changed poly adipate succinic acid ester into PTMG.Mechanics of materials intensity 28MPa, elongation at break 550%.
From embodiment and Comparative Examples more as can be seen, adopt polyether/polyester mixings dibasic alcohol to improve the mechanical strength of material, reach more than the 40MPa, and raising material elongation at break, reached 600%～700%.The used polyester type polyurethane material mechanical property of " polyesterurethane condom " that discloses among the CN1142838A is as follows: intensity 5100Psi (about 36MPa), elongation at break is 550%.Polyether/polyester type polyurethane material performance of the present invention surpasses above-mentioned materials.Therefore the present invention adopt mix that the macromolecular diol technology can obtain that intensity is higher, elasticity and snappiness and feel better material.
Embodiment eight:
Present embodiment and following enforcement just are the embodiment of condom preparation.
(1) solution preparation joins the polyether/polyester type polyurethane sizing material in the mixed solvent of being made up of by 9: 1 proportionings N,N-DIMETHYLACETAMIDE and tetrahydrofuran (THF) at normal temperatures, constantly stir and be made into the solution that concentration is 8% (weight), after treating that sizing material dissolves fully, filter stand-by.
(2) dipping will be water clean up, and the standby condom core in dry back immerses the glue 50 seconds after the filtration at normal temperatures, takes out dry then.The dipping number of times of present embodiment 3 times.
(3) dry behind first and second time dipping, respectively 45 ℃ dry 10 minutes down, after dipping finishes for the third time, promptly 85 ℃ dry 30 minutes down.
(4) demoulding is cooled to the demoulding after the room temperature.
Embodiment nine:
(1) the solution preparation joins the polyether/polyester type polyurethane sizing material at normal temperatures by dimethyl formamide, tetrahydrofuran (THF) and N,N-DIMETHYLACETAMIDE, and constantly stir in the mixed solvent by 10: 85: 5 proportionings compositions, be made into the solution that concentration is 10% (weight), after treating that sizing material dissolves fully, filter stand-by.
(2) dipping will be water clean up, and the standby condom core in dry back immerses 30 seconds of glue after the filtration at normal temperatures, takes out dry then.The dipping number of times of present embodiment 2 times.
(3) drying behind the dry dipping for the first time is to carry out under 40 ℃ 20 minutes, after dipping finishes for the second time, promptly 85 ℃ dry 35 minutes down.
(4) the dry postcooling of demoulding demoulding to the room temperature.
Embodiment ten:
(1) solution preparation joins the polyether/polyester type polyurethane sizing material constantly stirring in the mixed solvent of forming by dioxane, tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) and by 10: 80: 10 proportioning at normal temperatures, be made into the solution that concentration is 6% (weight), after treating that sizing material dissolves fully, filter stand-by.
(2) the condom core after dipping will be handled immerses 40 seconds of glue after the filtration at normal temperatures, takes out dry then.The dipping number of times of present embodiment 4 times.
(3) drying between dry dipping is to carry out under 48 ℃ 15 minutes, after the 4th dipping finishes, promptly 80 ℃ dry 35 minutes down.
(4) demoulding and previous embodiment are omited together.
Embodiment 11:
(1) the solution preparation joins by dimethyl formamide, tetrahydrofuran (THF) and dioxane the polyether/polyester type polyurethane sizing material at normal temperatures by constantly stirring in the mixed solvent that also 10: 80: 10 proportioning is formed, be made into the solution that concentration is 5% (weight), after treating that sizing material dissolves fully, filter stand-by.
(2) the condom core after dipping will be handled immerses 50 seconds of glue after the filtration at normal temperatures, takes out dry then.The dipping number of times of present embodiment 5 times.
(3) drying between dry per twice dipping is to carry out under 40 ℃ 10 minutes, and is following dry 45 minutes at 85 ℃ after last dipping finishes.
(4) demoulding is the same, slightly.
Embodiment 12:
(1) solution preparation joins the polyether/polyester type polyurethane sizing material constantly stirring in the mixed solvent of forming by N,N-DIMETHYLACETAMIDE, tetrahydrofuran (THF) and dimethyl sulfoxide (DMSO) and by 7: 85: 8 proportioning at normal temperatures, be made into the solution of concentration 8% (weight), after treating that sizing material dissolves fully, filter stand-by.
(2) the condom core after dipping will be handled immerses 35 seconds of glue after the filtration at normal temperatures, takes out dry then.Present embodiment dipping number of times 3 times.
(3) drying between dry per twice dipping is to carry out under 50 ℃ 8 minutes, and is following dry 30 minutes at 90 ℃ behind last dipping.
(4) demoulding is the same, slightly.
Embodiment 13:
(1) solution preparation joins the polyether/polyester type polyurethane sizing material constantly stirring in the mixed solvent of forming by dioxane, dimethyl sulfoxide (DMSO) and dimethyl formamide and by 60: 10: 30 proportioning at normal temperatures, be made into the solution that concentration is 6.5% (weight), after treating that sizing material dissolves fully, filter stand-by.
(2) the condom core after will handling immerses 45 seconds of glue after the filtration at normal temperatures, takes out dry then.Present embodiment dipping number of times 4 times.
(3) drying between dry per twice dipping is to carry out under 45 ℃ 12 minutes, last dipping back 90 ℃ dry 40 minutes down.
(4) demoulding is the same, slightly.
Claims (8)
1. the preparation method of a polyether/polyester type polyurethane material contains vulcabond in its prescription, and polyester polyol, chainextender, lubricant and oxidation inhibitor is characterized in that also containing polyether glycol, the ratio range of each component following (weight percent):
Vulcabond 19～27%
Polyether glycol 23～45%
Polyester polyol 24～48%
Chainextender 1～8%
Lubricant 1～5%
During oxidation inhibitor 1～5% preparation, adding polyether glycol, polyester polyol mix under 50～80 ℃ earlier; Add vulcabond again, 60～90 ℃ of following prepolymerization reactions 30～50 minutes; And then add chainextender, lubricant, oxidation inhibitor and put into screw extrusion press after mixing, extrude after 2～5 minutes 100～210 ℃ of following polyreactions, and cooling, pelletizing, drying.
2. the preparation method of polyether/polyester type polyurethane material according to claim 1 is characterized in that vulcabond also can select any in tolylene diisocyanate, ethylbenzene vulcabond, six methylene diisocyanates for use.
3. the preparation method of polyether/polyester type polyurethane material according to claim 1 is characterized in that polyester polyol also can select any in polyethylene glycol adipate, poly-adipate glycol propylene glycol ester, the poly-adipate glycol butanediol ester for use.
4. the preparation method of polyether/polyester type polyurethane material according to claim 1 is characterized in that polyether glycol can select polypropylene oxide glycol, polyethylene oxide glycol, polyoxyethylene oxypropylene copolyether glycol, THF for use---equal any in polyethers glycol, the polybutene glycol.
5. according to the preparation method of claim 1 or 2 or 3 or 4 described polyether/polyester type polyurethane materials, it is characterized in that lubricant can select methyl-silicone oil, hydroxy silicon oil, oxyethyl group silicone oil for use; Oxidation inhibitor can be selected Lrganoxlolo, Tinuvinp (Chiba-Geigr), 2,6,4 oxidation inhibitor, 2,6-di-tert-butyl cresols, 2,5-dialkyl group quinhydrones, antioxidant 300 for use.
6. the preparation method of a polyether/polyester type polyurethane condom is characterized in that its forming process flow process is solution preparation → dipping → drying → demoulding, and the processing condition of each operation of this flow process should be controlled to be:
(1) the solution preparation joins the polyether/polyester type polyurethane sizing material in the mixed solvent by 5～10% (weight) proportioning, constantly stirs at normal temperatures, and is stand-by after making it to dissolve fully and filtering;
(2) dipping will be water clean up, and the standby condom core in dry back immersed in the polyether/polyester type polyurethane solution 30～50 seconds at normal temperatures, took out dryly then, can flood repeatedly;
(3) dry drying between per twice dipping is to carry out under 40～50 ℃ 8～20 minutes, and is following dry 30～50 minutes at 80～110 ℃ after last dipping finishes;
Demoulding when (4) the dry postcooling of the demoulding is to room temperature.
7. the preparation method of polyether/polyester type polyurethane condom according to claim 6 is characterized in that mixed solvent can be selected for use and appoints two or more in dimethyl formamide, N,N-DIMETHYLACETAMIDE, dioxane, dimethyl sulfoxide (DMSO), the tetrahydrofuran (THF).
8. according to the preparation method of claim 6 or 7 described polyether/polyester type polyurethane condoms, it is characterized in that flooding number of times is 1～5 time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00109920 CN1111181C (en) | 2000-07-14 | 2000-07-14 | Polyether/polyester type polyurethane material and process for preparing condom from it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00109920 CN1111181C (en) | 2000-07-14 | 2000-07-14 | Polyether/polyester type polyurethane material and process for preparing condom from it |
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| Publication Number | Publication Date |
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| CN1304944A true CN1304944A (en) | 2001-07-25 |
| CN1111181C CN1111181C (en) | 2003-06-11 |
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| CN 00109920 Expired - Fee Related CN1111181C (en) | 2000-07-14 | 2000-07-14 | Polyether/polyester type polyurethane material and process for preparing condom from it |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101961279A (en) * | 2010-11-05 | 2011-02-02 | 胡智强 | Double-layer sandwich or multi-layer sandwich multi-latex condom and preparation method thereof |
| CN102181031A (en) * | 2010-10-20 | 2011-09-14 | 上海汇得化工有限公司 | Durable polyurethane resin for sofa leather and preparation method of the durable polyurethane resin |
| CN106280396A (en) * | 2016-08-30 | 2017-01-04 | 上海强睿博高分子科技有限公司 | Condom for women and preparation method thereof |
| WO2017036177A1 (en) * | 2015-09-02 | 2017-03-09 | 上海强睿博高分子科技有限公司 | Condom demolding method |
| CN107296677A (en) * | 2017-07-10 | 2017-10-27 | 海氏海诺乳胶（青岛）有限公司 | A kind of manufacture method of fine and close inner membrance graphene sheath |
| CN108095882A (en) * | 2017-04-06 | 2018-06-01 | 海氏海诺乳胶（青岛）有限公司 | A kind of high resiliency skin softening type polyurethane sheath and its manufacturing method |
| CN108099075A (en) * | 2017-04-06 | 2018-06-01 | 海氏海诺乳胶（青岛）有限公司 | A kind of reinforced polyurethane condom of high draw ratio toughness and its manufacturing method |
| CN111808260A (en) * | 2020-07-29 | 2020-10-23 | 四川尤博瑞新材料有限公司 | Thermosensitive condom based on waterborne polyurethane and preparation method thereof |
| CN114096290A (en) * | 2019-06-28 | 2022-02-25 | 尤达莫恩科技私人有限公司 | Molded polyurethane hydrogels |
| CN116199855A (en) * | 2023-05-06 | 2023-06-02 | 成都瑞吉龙科技有限责任公司 | Polyether-polyester mixed polyurethane and preparation method thereof |
-
2000
- 2000-07-14 CN CN 00109920 patent/CN1111181C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102181031A (en) * | 2010-10-20 | 2011-09-14 | 上海汇得化工有限公司 | Durable polyurethane resin for sofa leather and preparation method of the durable polyurethane resin |
| CN102181031B (en) * | 2010-10-20 | 2012-12-19 | 上海汇得化工有限公司 | Durable polyurethane resin for sofa leather and preparation method of the durable polyurethane resin |
| CN101961279A (en) * | 2010-11-05 | 2011-02-02 | 胡智强 | Double-layer sandwich or multi-layer sandwich multi-latex condom and preparation method thereof |
| WO2017036177A1 (en) * | 2015-09-02 | 2017-03-09 | 上海强睿博高分子科技有限公司 | Condom demolding method |
| CN106280396A (en) * | 2016-08-30 | 2017-01-04 | 上海强睿博高分子科技有限公司 | Condom for women and preparation method thereof |
| CN106280396B (en) * | 2016-08-30 | 2018-08-31 | 浙江强睿博高分子科技有限公司 | Sheath for women and preparation method thereof |
| CN108095882A (en) * | 2017-04-06 | 2018-06-01 | 海氏海诺乳胶（青岛）有限公司 | A kind of high resiliency skin softening type polyurethane sheath and its manufacturing method |
| CN108099075A (en) * | 2017-04-06 | 2018-06-01 | 海氏海诺乳胶（青岛）有限公司 | A kind of reinforced polyurethane condom of high draw ratio toughness and its manufacturing method |
| CN107296677A (en) * | 2017-07-10 | 2017-10-27 | 海氏海诺乳胶（青岛）有限公司 | A kind of manufacture method of fine and close inner membrance graphene sheath |
| CN114096290A (en) * | 2019-06-28 | 2022-02-25 | 尤达莫恩科技私人有限公司 | Molded polyurethane hydrogels |
| CN111808260A (en) * | 2020-07-29 | 2020-10-23 | 四川尤博瑞新材料有限公司 | Thermosensitive condom based on waterborne polyurethane and preparation method thereof |
| CN111808260B (en) * | 2020-07-29 | 2021-05-25 | 四川尤博瑞新材料有限公司 | Thermosensitive condom based on waterborne polyurethane and preparation method thereof |
| CN116199855A (en) * | 2023-05-06 | 2023-06-02 | 成都瑞吉龙科技有限责任公司 | Polyether-polyester mixed polyurethane and preparation method thereof |
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