CN104693405B - A kind of super branched polyurethane and preparation method thereof containing active amino - Google Patents
A kind of super branched polyurethane and preparation method thereof containing active amino Download PDFInfo
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- CN104693405B CN104693405B CN201510141212.6A CN201510141212A CN104693405B CN 104693405 B CN104693405 B CN 104693405B CN 201510141212 A CN201510141212 A CN 201510141212A CN 104693405 B CN104693405 B CN 104693405B
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- 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
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
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- 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
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- 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
- C08G18/30—Low-molecular-weight compounds
- C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
- C08G18/3203—Polyhydroxy compounds
- C08G18/3206—Polyhydroxy compounds aliphatic
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- 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
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4081—Mixtures of compounds of group C08G18/64 with other macromolecular compounds
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- 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
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- 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
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
-
- 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
- C08G18/48—Polyethers
- C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
-
- 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
- C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
- C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
Abstract
The invention discloses a kind of super branched polyurethane and preparation method thereof containing active amino, preparation method first mixes polyether polyol with diisocyanate, it is stirred to react, catalyst is added, using aprotic organic solvent as solvent, after reacting a period of time, small molecule chain extender is added, carries out chain extension, is eventually adding end-capping reagent, carry out partially end-blocked, obtained linear polyester performed polymer；Then Hyperbranched Polymer with Terminal Amido is mixed with linear polyester performed polymer, it is stirred to react, super branched polyurethane is made, super branched polyurethane resin synthesized by the present invention contains a large amount of active amino and imino group, the sanitation performance of polyurethane film not only can be improved, but also dyeability can be improved.
Description
Technical field
The present invention relates to polyurethane material processing technique field, in particular to a kind of hyperbranched poly ammonia containing active amino
Ester and preparation method thereof.
Background technique
Dissaving polymer attracts attention because of its unique structure and physicochemical properties.It has been widely used
It is led in coating, the modified additive of resin and processing agent, crosslinking agent, drug and genophore, nanotechnology, supermolecule science etc.
Domain.
Polyurethane (PU) is that have intensity height containing the macromolecular compound for repeating carbamate groups on main chain, resistance to
Mill, low temperature resistant, chemical-resistant resistance, the properties such as resilience is excellent have been widely used in PU synthetic leather, leather finishing agent and spinning
In fabric coating.Although solvent type dry method polyurethane film excellent in mechanical performance, the surface compact of film, steam are difficult to penetrate, and
Hydrophilic radical is few in molecule segment, poor to the compatibility of water, and moisture absorption venting capability is poor, causes the comfort of finished product poor.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the purpose of the present invention is to provide a kind of hyperbranched polies containing amino
Urethane and preparation method thereof overcomes the defect of existing polyurethane film sucting wet air permeability difference.
To achieve the goals above, the technical solution adopted by the present invention is that:
A kind of preparation method of the super branched polyurethane containing active amino, comprising the following steps:
1) polyether polyol is dissolved in the aprotic organic solvent after drying, under conditions of nitrogen protection, is added dropwise two
Simultaneously catalyst is added in isocyanates, is stirred to react 1~2h at 75~85 DEG C；Then small molecule chain extender is added, 75~85
It is stirred to react 2~3h at DEG C, carries out chain extension；It is eventually adding end-capping reagent, 1~2h is stirred to react at 70~80 DEG C, carries out part
Linear polyester performed polymer is made in sealing end；Wherein, polyether polyol and the mass ratio of the aprotic organic solvent after drying are 1:
Diisocyanate is added dropwise in 1.5~1:2, the ratio that the mass ratio of the material according to-NCO and-OH is 2.5:1~3:1；
2) Hyperbranched Polymer with Terminal Amido is mixed with linear polyester performed polymer and is reacted, reaction temperature is 0
~25 DEG C, 0.5~2.5h of reaction time obtains thick liquid；Wherein, Hyperbranched Polymer with Terminal Amido with it is dry after non-proton have
The mass ratio of solvent is 1:4~1:5 ,-NH in the Hyperbranched Polymer with Terminal Amido and linear polyester performed polymer2With-NCO
Molar ratio be 1:1~1:2.
3) by the thick liquid, with ethyl alcohol, acetone washing, vacuum drying obtains super branched polyurethane.
As a further improvement of the present invention, in the step 1), polyether polyol is polytetrahydrofuran ether glycol, poly- second
Glycol or polypropylene glycol, number-average molecular weight are 1000.
As a further improvement of the present invention, in the step 1) and step 2), aprotic organic solvent N, N- diformazan
Base formamide, n,N-dimethylacetamide, N- methyl-pyrrolidon or acetone, wherein used in step 1) and step 2)
Aprotic organic solvent is same or different.
As a further improvement of the present invention, the diisocyanate is isophorone diisocyanate, toluene diisocyanate
Acid esters or diphenyl methane -4,4 ‵-diisocyanate.
As a further improvement of the present invention, the catalyst is dibutyl tin dilaurate；The additional amount of catalyst is
The 0.007% of diisocyanate and polyether polyol gross mass.
As a further improvement of the present invention, in the step 1), small molecule chain extender be 1,4-butanediol, 1,6- oneself two
Alcohol；Small molecule chain extender is added dropwise in the ratio that the mass ratio of the material according to-NCO and-OH is 1:1.1~1:1.2.
As a further improvement of the present invention, in the step 1), end-capping reagent is methanol, ethyl alcohol；According to-NCO's and-OH
End-capping reagent is added dropwise in the ratio that the mass ratio of the material is 1:1~1:1.1.
As a further improvement of the present invention, linear polyester performed polymer structural formula made from the step 1) is as follows:
A kind of super branched polyurethane containing active amino, the hyperbranched poly containing amino as described in any of the above one
It is prepared by the preparation method of urethane.
As a further improvement of the present invention, the super branched polyurethane structural formula containing active amino is as follows:
Wherein,
R1For
Compared with prior art, the invention has the following advantages that
Preparation method of the invention has the amine-terminated hyperbranced of branched structure by introducing into linear polyester performed polymer
Fluidized polymer makes super branched polyurethane obtained contain a large amount of active aminos and imino group, not only increases dyestuff binding site, make
Anionic dye and positively charged amino with ionic bond in conjunction with and enhance coloration, improve the dyeability of polyurethane film
Energy；Active hydrophilic radical amount is increased simultaneously, improves sanitation performance.This method is simple, and reaction is mild, easy to operate.Increase
Active hydrophilic radical amount, moisture absorption venting capability are strong.
The super branched polyurethane containing amino of preparation of the invention, super branched polyurethane obtained contain a large amount of active ammonias
Base and imino group, excellent in mechanical performance, the surface porosity of film, steam is easy to penetrate, and hydrophilic radical is more in molecule segment,
Good to the compatibility of water, moisture absorption venting capability is strong, and the comfort of finished product is strong.
Detailed description of the invention
Fig. 1 is the synthetic reaction schematic diagram of base polyurethane prepolymer for use as.
Fig. 2 is the synthetic reaction schematic diagram of super branched polyurethane.
Attached drawing 1 and Fig. 2 are the reaction equations that the super branched polyurethane containing amino is prepared by taking IPDI and PTMG1000 as an example.
Specific embodiment
The present invention is described in further details below with reference to embodiment.
Embodiment 1:
As depicted in figs. 1 and 2, a kind of preparation method of the super branched polyurethane containing amino, includes the following steps:
1) N, N- that 10.00g polytetrahydrofuran ether glycol 1000 (being abbreviated as PTMG1000) is dissolved in after 15ml drying are weighed
In dimethylformamide (being abbreviated as DMF)；
It 2) is 2.5:1 according to the mass ratio of the material of-NCO and-OH, with 0.007% 2 laurel under conditions of nitrogen protection
Sour dibutyl tin (being abbreviated as DBTDL) be catalyst, be added dropwise 5.55g isophorone diisocyanate (being abbreviated as IPDI) make its with
Polyether polyol is stirred to react 1.5h at 85 DEG C, and 0.81g1 is then added, and 4- butanediol is stirred to react 2.5h at 85 DEG C,
Carry out chain extension；It is eventually adding 0.37g dehydrated alcohol, 2h is stirred to react at 80 DEG C, carries out partially end-blocked, obtained linear polyester
Performed polymer；
It 3) is 1:1.1 according to the molar ratio of Hyperbranched Polymer with Terminal Amido and linear polyester performed polymer, reaction temperature is 5
DEG C, reaction time 1.5h obtains thick liquid.
4) by thick liquid obtained in step 3, with ethyl alcohol, acetone washing, vacuum drying obtains super branched polyurethane.
Embodiment 2:
A kind of preparation method of the super branched polyurethane containing amino, preparation flow reference such as Fig. 1 and Fig. 2, including it is as follows
Step:
1) N that 10.00g cetomacrogol 1000 (being abbreviated as PEG1000) is dissolved in after 15ml drying, N- dimethylacetamide are weighed
In amine (being abbreviated as DMAC)；
It 2) is 2.5:1 according to the mass ratio of the material of-NCO and-OH, with 0.007% 2 laurel under conditions of nitrogen protection
Sour dibutyl tin (being abbreviated as DBTDL) is catalyst, and 4.35g toluene di-isocyanate(TDI) (being abbreviated as TDI), which is added dropwise, makes itself and polyethers
Polyalcohol is stirred to react 1.5h at 85 DEG C, and 0.81g1 is then added, and 4- butanediol is stirred to react 2.5h at 85 DEG C, carries out
Chain extension；It is eventually adding 0.37g dehydrated alcohol, 2h is stirred to react at 80 DEG C, carries out partially end-blocked, obtained linear polyester pre-polymerization
Body；
It 3) is 1:1.15 according to the molar ratio of Hyperbranched Polymer with Terminal Amido and linear polyester performed polymer, reaction temperature exists
10 DEG C, reaction time 1h obtains thick liquid.
4) by thick liquid obtained in step 3, with ethyl alcohol, acetone washing, vacuum drying obtains super branched polyurethane
Embodiment 3:
A kind of preparation method of the super branched polyurethane containing amino, preparation flow reference such as Fig. 1 and Fig. 2, including it is as follows
Step:
1) N that 10.00g polypropylene glycol 1000 (being abbreviated as PPG1000) is dissolved in after 15ml drying, N- dimethyl formyl are weighed
In amine (being abbreviated as DMF)；
It 2) is 3:1 according to the mass ratio of the material of-NCO and-OH, with 0.007% tin dilaurate under conditions of nitrogen protection
Dibutyl tin (being abbreviated as DBTDL) is catalyst, and 6.66g isophorone diisocyanate (being abbreviated as IPDI), which is added dropwise, to be made it and gather
Ethoxylated polyhydric alcohol is stirred to react 1.5h at 85 DEG C, and 1.08g1 is then added, and 4- butanediol is stirred to react 2.5h at 85 DEG C, into
Row chain extension；It is eventually adding 0.46g dehydrated alcohol, 2h is stirred to react at 80 DEG C, progress is partially end-blocked, and it is pre- that linear polyester is made
Aggressiveness；
It 3) is 1:1.1 according to the molar ratio of Hyperbranched Polymer with Terminal Amido and linear polyester performed polymer, reaction temperature is 5
DEG C, reaction time 1.5h obtains thick liquid.
4) by thick liquid obtained in step 3), with ethyl alcohol, acetone washing, vacuum drying obtains super branched polyurethane
Embodiment 4:
A kind of preparation method of the super branched polyurethane containing amino, preparation flow reference such as Fig. 1 and Fig. 2, including it is as follows
Step:
1) N, N- that 10.00g polytetrahydrofuran ether glycol 1000 (being abbreviated as PTMG1000) is dissolved in after 10ml drying are weighed
In dimethylformamide (being abbreviated as DMF)；
It 2) is 2.55:1 according to the mass ratio of the material of-NCO and-OH, with 0.007% February under conditions of nitrogen protection
Dilaurylate (being abbreviated as DBTDL) is catalyst, and 4.437g toluene di-isocyanate(TDI) (being abbreviated as TDI), which is added dropwise, to be made it and gather
Ethoxylated polyhydric alcohol is stirred to react 1.5h at 85 DEG C, and 1.42g1 is then added, and 6- hexylene glycol is stirred to react 2.5h at 85 DEG C, into
Row chain extension；It is eventually adding 0.32g anhydrous methanol, 2h is stirred to react at 80 DEG C, progress is partially end-blocked, and it is pre- that linear polyester is made
Aggressiveness；
It 3) is 1:1.2 according to the molar ratio of Hyperbranched Polymer with Terminal Amido and linear polyester performed polymer, reaction temperature exists
15 DEG C, reaction time 0.5h obtains thick liquid.
4) by thick liquid obtained in step 3, with ethyl alcohol, acetone washing, vacuum drying obtains super branched polyurethane.
Wherein, the Hyperbranched Polymer with Terminal Amido in embodiment is specifically as follows
Claims (2)
1. a kind of preparation method of the super branched polyurethane containing active amino, which comprises the following steps:
1) polyether polyol is dissolved in the aprotic organic solvent after drying, under conditions of nitrogen protection, two isocyanides is added dropwise
Acid esters and the catalyst dibutyltin dilaurylate that diisocyanate and polyether polyol gross mass 0.007% is added, 75~
1~2h is stirred to react at 85 DEG C；Then small molecule chain extender is added dropwise, 2~3h is stirred to react at 75~85 DEG C, carries out chain extension；
It is eventually adding end-capping reagent, 1~2h is stirred to react at 70~80 DEG C, progress is partially end-blocked, is made single-ended for the linear poly- of-NCO
Urethane performed polymer；Wherein, the mass ratio of polyether polyol and the aprotic organic solvent after drying is 1:1.5~1:2, according to-
Diisocyanate is added dropwise in the ratio that the mass ratio of the material of NCO and-OH is 2.5:1~3:1；
Wherein, polyether polyol is polytetrahydrofuran ether glycol, polyethylene glycol or polypropylene glycol, and number-average molecular weight is
1000；The diisocyanate is -4,4 ‵-two of isophorone diisocyanate, toluene di-isocyanate(TDI) or diphenyl methane
Isocyanates；Small molecule chain extender is 1,4- butanediol, 1,6-HD；End-capping reagent is methanol, ethyl alcohol；It is dripped according to following dosage
Add small molecule chain extender and end-capping reagent:
10.00g polytetrahydrofuran ether glycol 1000；The mass ratio of the material according to-NCO and-OH is 2.5:1, and the different Buddhist of 5.55g is added dropwise
That ketone diisocyanate, is then added 0.81g1,4- butanediol is eventually adding 0.37g dehydrated alcohol；Alternatively,
10.00g cetomacrogol 1000；The mass ratio of the material according to-NCO and-OH is 2.5:1, and 4.35g toluene diisocynate is added dropwise
Ester, is then added 0.81g1, and 4- butanediol is eventually adding 0.37g dehydrated alcohol；Alternatively,
10.00g polypropylene glycol 1000；The mass ratio of the material according to-NCO and-OH is 3:1, and two isocyanide of 6.66g isophorone is added dropwise
Then 1.08g1,4- butanediol is added in acid esters；It is eventually adding 0.46g dehydrated alcohol；
2) Hyperbranched Polymer with Terminal Amido is mixed with linear polyester performed polymer and is reacted, reaction temperature is at 0~25 DEG C, instead
0.5~2.5h between seasonable, obtains thick liquid；Wherein, Hyperbranched Polymer with Terminal Amido and the aprotic organic solvent after drying
Mass ratio is 1:4~1:5 ,-NH in the Hyperbranched Polymer with Terminal Amido and linear polyester performed polymer2With the molar ratio of-NCO
For 1:1~1:2；
3) by the thick liquid, with ethyl alcohol, acetone washing, vacuum drying obtains super branched polyurethane；
In the step 1) and step 2), aprotic organic solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, N-
Methyl-pyrrolidon or acetone, wherein step 1) and aprotic organic solvent used in step 2) are same or different.
2. the super branched polyurethane containing active amino made from a kind of preparation method according to claim 1.
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| CN105542108B (en) * | 2015-12-22 | 2018-02-27 | 上海华峰超纤材料股份有限公司 | Superfine fiber chemical leather easy dyeing polyurethane resin and preparation method thereof |
| CN105670014A (en) * | 2016-01-14 | 2016-06-15 | 陕西科技大学 | Preparation method of moisture-absorbing and breathable polyurethane membrane |
| WO2017214745A1 (en) * | 2016-06-13 | 2017-12-21 | 杨磊 | Process for preparing hyperbranched polyurethane |
| CN106349452B (en) * | 2016-08-19 | 2019-01-25 | 陕西科技大学 | Hold the preparation method of fluoroalkyl super branched polyurethane nano hybridization leather finishing agent |
| CN106366275B (en) * | 2016-10-20 | 2019-02-26 | 湖北大学 | A kind of heat resistance super branched polyurethane and preparation method thereof |
| CN107033320A (en) * | 2017-03-31 | 2017-08-11 | 优美特（北京）环境材料科技股份公司 | Hydroxyl water-borne dispersions and preparation method thereof |
| KR101959146B1 (en) * | 2017-12-27 | 2019-03-15 | 효성티앤씨 주식회사 | Elastic fiber having improved dying property, and method of manufacturing the same |
| CN109880060B (en) * | 2019-02-01 | 2021-08-27 | 浙江材华科技有限公司 | Dendritic waterborne polyurethane-based high-molecular dye and preparation method thereof |
| CN111608020B (en) * | 2020-04-29 | 2021-12-31 | 仙鹤股份有限公司 | Super-soft medical crepe paper and preparation method thereof |
| CN112225919B (en) * | 2020-09-11 | 2023-07-25 | 王平 | Geomembrane for soil remediation engineering and preparation method thereof |
| CN113663539B (en) * | 2021-09-16 | 2022-11-01 | 西安热工研究院有限公司 | Hyperbranched antibacterial polyurethane reverse osmosis membrane and preparation method thereof |
| CN115232542B (en) * | 2022-07-21 | 2024-01-02 | 宁波爱甬新材料科技有限公司 | Graphene anticorrosive paint and preparation method thereof |
| CN116947404B (en) * | 2023-05-10 | 2024-04-16 | 湖南中大设计院有限公司 | Concrete for mountain gas tunnel and preparation method thereof |
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| CN104356354A (en) * | 2014-11-17 | 2015-02-18 | 陕西科技大学 | Preparation method of chromatophilous polyurethane applied to superfine fiber synthetic leather |
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| CN104356354A (en) * | 2014-11-17 | 2015-02-18 | 陕西科技大学 | Preparation method of chromatophilous polyurethane applied to superfine fiber synthetic leather |
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| 超支化聚氨酯的研究进展;王学川等;《西部皮革》;20090430;第31卷(第7期);3-7 |
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