CN105088798A - Aqueous polyurethane sizing agent and preparation method thereof - Google Patents
Aqueous polyurethane sizing agent and preparation method thereof Download PDFInfo
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- CN105088798A CN105088798A CN201510568396.4A CN201510568396A CN105088798A CN 105088798 A CN105088798 A CN 105088798A CN 201510568396 A CN201510568396 A CN 201510568396A CN 105088798 A CN105088798 A CN 105088798A
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- aqueous polyurethane
- sizing agent
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Abstract
The present invention relates to the technical field of carbon fiber sizing, and more particularly relates to an aqueous polyurethane sizing agent and a preparation method thereof. The aqueous polyurethane sizing agent comprises the following ingredients by weight: 5-25 parts of aqueous polyurethane emulsion and 75-95 parts of deionized water. The preparation method of the aqueous polyurethane sizing agent comprises the steps of: (1) preparing an aqueous polyurethane prepolymer; (2) adding deionized water to the aqueous polyurethane prepolymer to obtain an aqueous polyurethane emulsion; and (3) adding deionized water into the aqueous polyurethane emulsion by weight ratio, and stirring evenly to obtain an aqueous polyurethane sizing agent. The aqueous polyurethane sizing agent provided by the present invention has good dilution stability, increases the wetting ability of sizing agent for carbon fiber, is more conducive to adhering to the surface of the carbon fiber, so that the carbon composite fiber material shows better mechanical properties.
Description
Technical field
The present invention relates to carbon fiber sizing agent technical field, more specifically relate to a kind of aqueous polyurethane sizing agent and preparation method thereof.
Background technology
Carbon fiber has high strength, high-modulus, conduction, heat conduction, the characteristic such as high temperature resistant and corrosion-resistant, and it has a wide range of applications in the field such as national defence, Aero-Space as a kind of important advanced composite material reinforcement.But in composite material pultrusion process, carbon fiber surface easily occurs that lousiness can affect the bonding of same substrate resin (mostly being epoxy resin), is difficult to play enhancing, toughness reinforcing effect.At present, researcher mainly adopts the method applying one deck epoxy emulsion type sizing agent at carbon fiber surface, while elimination lousiness, increases the adhesive strength of carbon fiber with base material epoxy resin.And more and more favored in carbon fibre composite pultrusion field along with polyurethane resin, carbon fiber and matrix polyurethane resin can be made to have good bonding effect to preparing, thus the New Emulsion sizing agent the two connected as one propose new requirement.This New Emulsion sizing agent not only should containing being used for the bonding group of same polyurethane resin, but also basic group---the carbamate of polyurethane material should be contained, thus increase the wettability of emulsion pasting agent for carbon fiber, be more conducive to be attached to carbon fiber surface, make carbon fiber compound polyurethane material show better mechanical property.Some carbon fiber sizing agents involved by current Chinese patent and preparation method thereof, Problems existing is: (1) is all the method adopting outer emulsification mostly, by adding various emulsifying agent, solvent type resin is scattered in water and is prepared from, its storage stability is poor, and the toxic solvent used and can to environment; (2) sizing agent emulsion can be diluted into the system of solid content less than 5%, thus is easy to the precipitation causing active ingredient.
Summary of the invention
The object of the present invention is to provide the aqueous polyurethane sizing agent that a kind of environmentally friendly, good stability, especially dilution stability can meet the demands.
Another object of the present invention is to the preparation method that a kind of aqueous polyurethane sizing agent is provided.
In order to achieve the above object, the technical solution used in the present invention is:
A kind of aqueous polyurethane sizing agent, comprises the component of following weight portion:
Aqueous polyurethane emulsion: 5 ~ 25 parts, deionized water: 75 ~ 95 parts.
In such scheme, described aqueous polyurethane emulsion comprises the component of following weight portion:
Dihydroxylic alcohols: 110 ~ 135 parts, isocyanates: 15 ~ 40 parts, catalyst: 0 ~ 0.01 part,
Deionized water: 225 ~ 600 parts.
In such scheme, described dihydroxylic alcohols is the combination of the polyethylene glycol of number-average molecular weight 400 ~ 2000 and the PTMG of number-average molecular weight 400 ~ 2000;
Described isocyanates is isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI) or hexamethylene diisocyanate;
In described dihydroxylic alcohols, the molal quantity total amount of hydroxyl-OH and the molal quantity total amount of isocyanate group-NCO in isocyanates are than being [-OH]: [-NCO]=1.5:1 ~ 1:1.5.
In such scheme, described catalyst is dibutyl tin dilaurate.
In such scheme, the percetage by weight in the formation component of described aqueous polyurethane emulsion in addition to deionized water shared by polyethylene glycol is 5% ~ 50%.
A preparation method for aqueous polyurethane sizing agent, comprises the steps:
(1) Waterborne Polyurethane Prepolymer is prepared;
(2) add deionized water in hydrotropism's base polyurethane prepolymer for use as, obtain aqueous polyurethane emulsion;
(3) in hydrotropism's polyaminoester emulsion, ratio adds deionized water by weight, obtains aqueous polyurethane sizing agent after stirring.
In such scheme, described step (1) specifically comprises the steps:
The dihydroxylic alcohols of 110 ~ 135 weight portions is added in reaction vessel, after mixing, dehydration 20 ~ 30min is vacuumized under 120 DEG C of conditions, be cooled to 70 ~ 80 DEG C, add the catalyst reaction 3 ~ 6 hours of the isocyanates of 15 ~ 40 weight portions and 0 ~ 0.01 weight portion, be cooled to 40 ~ 50 DEG C, obtain the Waterborne Polyurethane Prepolymer that end group is oh group.
In such scheme, described step (2) specifically comprises the steps:
Be add deionized water in the Waterborne Polyurethane Prepolymer of oh group to end group under the high-speed stirred shearing force of 1200r/min ~ 2500r/min, obtain aqueous polyurethane emulsion.
Compared with prior art, the beneficial effect that the technical solution used in the present invention produces is as follows:
Aqueous polyurethane sizing agent provided by the invention belongs to the self-emulsifying systems of carbon fiber, preparation process is nontoxic, containing certain hydrophilic radical in molecular structure, there is good dilution stability, overcome the shortcoming of existing carbon fiber sizing agent, it is compared with common outer oil-in-water type carbon fiber sizing agent, not only containing being used for the bonding oh group of same polyurethane resin, but also basic group---the carbamate containing polyurethane material, thus add the wettability of sizing agent for carbon fiber, be more conducive to be attached to carbon fiber surface, carbon fibre composite is made to show better mechanical property.
Accompanying drawing explanation
The process chart of the preparation method of the aqueous polyurethane sizing agent that Fig. 1 provides for the embodiment of the present invention.
Detailed description of the invention
Below in conjunction with drawings and Examples, technical solution of the present invention is described in detail.
The invention provides a kind of aqueous polyurethane sizing agent, comprise the component of following weight portion: aqueous polyurethane emulsion: 5 ~ 25 parts, deionized water: 75 ~ 95 parts.
Further, described aqueous polyurethane emulsion comprises the component of following weight portion: dihydroxylic alcohols: 110 ~ 135 parts, isocyanates: 15 ~ 40 parts, catalyst: 0 ~ 0.01 part, deionized water: 225 ~ 600 parts.
Particularly, described dihydroxylic alcohols is the combination of the polyethylene glycol of number-average molecular weight 400 ~ 2000 and the PTMG of number-average molecular weight 400 ~ 2000; Described isocyanates is isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI) or hexamethylene diisocyanate; In described dihydroxylic alcohols, the molal quantity total amount of hydroxyl-OH and the molal quantity total amount of isocyanate group-NCO in isocyanates are than being [-OH]: [-NCO]=1.5:1 ~ 1:1.5; Described catalyst is dibutyl tin dilaurate.
Further, the percetage by weight in the formation component of described aqueous polyurethane emulsion in addition to deionized water shared by polyethylene glycol is 5% ~ 50%.
As shown in Figure 1, the present invention also provides a kind of preparation method of aqueous polyurethane sizing agent, comprises the steps:
Step 110: prepare Waterborne Polyurethane Prepolymer;
Described step 110 specifically comprises, the dihydroxylic alcohols of 110 ~ 135 weight portions is added in reaction vessel, after mixing, dehydration 20 ~ 30min is vacuumized under 120 DEG C of conditions, be cooled to 70 ~ 80 DEG C, add the catalyst reaction 3 ~ 6 hours of the isocyanates of 15 ~ 40 weight portions and 0 ~ 0.01 weight portion, be cooled to 40 ~ 50 DEG C, obtain the Waterborne Polyurethane Prepolymer that end group is oh group.
Step 120: add deionized water in hydrotropism's base polyurethane prepolymer for use as, obtain aqueous polyurethane emulsion;
Described step 120 specifically comprises, and is add deionized water in the Waterborne Polyurethane Prepolymer of oh group, obtains aqueous polyurethane emulsion under the high-speed stirred shearing force of 1200r/min ~ 2500r/min to end group.
Step 130: in hydrotropism's polyaminoester emulsion, ratio adds deionized water by weight, obtains aqueous polyurethane sizing agent after stirring.
Below by specific embodiment, the present invention will be described.
Embodiment 1
To in the 500ml four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed, add the PTMG of 70g weight portion, the polyethylene glycol of 60g weight portion, after mixing, under the condition of 120 DEG C, after vacuumizing dehydration 30min, be cooled to 70 DEG C, add the isoflurane chalcone diisocyanate of 22g weight portion and the dibutyl tin dilaurate of 0.005g weight portion, control reaction temperature 70 DEG C, reaction 3h, be cooled to 50 DEG C, pour the deionized water of 350g weight portion into, under 1200r/min condition, high shear dispersion, obtains aqueous polyurethane emulsion.
Get above-mentioned aqueous polyurethane emulsion 50g weight portion, add in stirred tank, add deionized water 450g weight portion under continuous stirring, discharging after stirring, obtain carbon fiber use polyurethane sizing agent (being numbered 1#).
Embodiment 2
To electric mixer is housed, in the 500ml four-hole boiling flask of reflux condensing tube and thermometer, add the PTMG of 84.5g weight portion, the polyethylene glycol of 45.5g weight portion, after mixing, under the condition of 120 DEG C, after vacuumizing dehydration 30min, be cooled to 70 DEG C, add the isoflurane chalcone diisocyanate of 22g weight portion and the dibutyl tin dilaurate of 0.005g weight portion, control reaction temperature 70 DEG C, reaction 3h, be cooled to 50 DEG C, pour the deionized water of 350g weight portion into, high shear dispersion under 1200r/min condition, obtain aqueous polyurethane emulsion.
Get above-mentioned aqueous polyurethane emulsion 50g weight portion, add in stirred tank, add deionized water 450g weight portion under continuous stirring, discharging after stirring, obtain carbon fiber use polyurethane sizing agent (being numbered 2#).
Embodiment 3
To electric mixer is housed, in the 500ml four-hole boiling flask of reflux condensing tube and thermometer, add the PTMG of 99.5g weight portion, the polyethylene glycol of 30.5g weight portion, after mixing, under the condition of 120 DEG C, after vacuumizing dehydration 30min, be cooled to 70 DEG C, add the isoflurane chalcone diisocyanate of 22g weight portion and the dibutyl tin dilaurate of 0.005g weight portion, control reaction temperature 70 DEG C, reaction 3h, be cooled to 50 DEG C, pour the deionized water of 350g weight portion into, high shear dispersion under 1200r/min condition, obtain aqueous polyurethane emulsion.
Get above-mentioned aqueous polyurethane emulsion 50g weight portion, add in stirred tank, add deionized water 450g weight portion under continuous stirring, discharging after stirring, obtain carbon fiber use polyurethane sizing agent (being numbered 3#).
Embodiment 4
To electric mixer is housed, in the 500ml four-hole boiling flask of reflux condensing tube and thermometer, add the PTMG of 114.5g weight portion, the polyethylene glycol of 15.5g weight portion, after mixing, under the condition of 120 DEG C, after vacuumizing dehydration 30min, be cooled to 70 DEG C, add the isoflurane chalcone diisocyanate of 22g weight portion and the dibutyl tin dilaurate of 0.005g weight portion, control reaction temperature 70 DEG C, reaction 3h, be cooled to 50 DEG C, pour the deionized water of 350g weight portion into, high shear dispersion under 1200r/min condition, obtain aqueous polyurethane emulsion.
Get above-mentioned aqueous polyurethane emulsion 50g weight portion, add in stirred tank, add deionized water 450g weight portion under continuous stirring, discharging after stirring, obtain carbon fiber use polyurethane sizing agent (being numbered 4#).
Embodiment 5
To electric mixer is housed, in the 500ml four-hole boiling flask of reflux condensing tube and thermometer, add the PTMG of 95.5g weight portion, the polyethylene glycol of 30.5g weight portion, after mixing, under the condition of 120 DEG C, after vacuumizing dehydration 30min, be cooled to 70 DEG C, add the isoflurane chalcone diisocyanate of 26g weight portion and the dibutyl tin dilaurate of 0.005g weight portion, control reaction temperature 70 DEG C, reaction 3h, be cooled to 50 DEG C, pour the deionized water of 350g weight portion into, high shear dispersion under 1200r/min condition, obtain aqueous polyurethane emulsion.
Get above-mentioned aqueous polyurethane emulsion 50g weight portion, add in stirred tank, add deionized water 450g weight portion under continuous stirring, discharging after stirring, obtain carbon fiber use polyurethane sizing agent (being numbered 5#).
Embodiment 6
To electric mixer is housed, in the 500ml four-hole boiling flask of reflux condensing tube and thermometer, add the PTMG of 102.5g weight portion, the polyethylene glycol of 30.5g weight portion, after mixing, under the condition of 120 DEG C, after vacuumizing dehydration 30min, be cooled to 70 DEG C, add the isoflurane chalcone diisocyanate of 19g weight portion and the dibutyl tin dilaurate of 0.005g weight portion, control reaction temperature 70 DEG C, reaction 3h, be cooled to 50 DEG C, pour the deionized water of 350g weight portion into, high shear dispersion under 1200r/min condition, obtain aqueous polyurethane emulsion.
Get above-mentioned aqueous polyurethane emulsion 50g weight portion, add in stirred tank, add deionized water 450g weight portion under continuous stirring, discharging after stirring, obtain carbon fiber use polyurethane sizing agent (being numbered 6#).
Embodiment 7
To in the 500ml four-hole boiling flask that electric mixer, reflux condensing tube and thermometer are housed, add the PTMG of 70g weight portion, the polyethylene glycol of 60g weight portion, after mixing, under the condition of 120 DEG C, after vacuumizing dehydration 30min, be cooled to 70 DEG C, add the toluene di-isocyanate(TDI) of 17.4g weight portion and the dibutyl tin dilaurate of 0.005g weight portion, control reaction temperature 70 DEG C, reaction 3h, be cooled to 50 DEG C, pour the deionized water of 340g weight portion into, under 1200r/min condition, high shear dispersion, obtains aqueous polyurethane emulsion.
Get above-mentioned aqueous polyurethane emulsion 50g weight portion, add in stirred tank, add deionized water 450g weight portion under continuous stirring, discharging after stirring, obtain carbon fiber use polyurethane sizing agent (being numbered 7#).
Embodiment 8
To electric mixer is housed, in the 500ml four-hole boiling flask of reflux condensing tube and thermometer, add the PTMG of 70g weight portion, the polyethylene glycol of 60g weight portion, after mixing, under the condition of 120 DEG C, after vacuumizing dehydration 30min, be cooled to 70 DEG C, add the hexamethylene diisocyanate of 16.8g weight portion and the dibutyl tin dilaurate of 0.005g weight portion, control reaction temperature 70 DEG C, reaction 3h, be cooled to 50 DEG C, pour the deionized water of 338g weight portion into, high shear dispersion under 1200r/min condition, obtain aqueous polyurethane emulsion.
Get above-mentioned aqueous polyurethane emulsion 50g weight portion, add in stirred tank, add deionized water 450g weight portion under continuous stirring, discharging after stirring, obtain carbon fiber use polyurethane sizing agent (being numbered 8#).
Respectively with carbon fiber use polyurethane sizing agent (being numbered 1 ~ 8#) prepared by above example, without the carbon fiber of sizing agent, starching process has been carried out to the surface that Jilin company produces, dipping time is 20s, at 150 DEG C after dry removing moisture, respectively the carbon fiber anti-wear performance before and after starching and carbon fibre composite boundary strength are tested.
Result is as following table:
Can find out, after using aqueous polyurethane sizing agent of the present invention to carry out starching process to carbon fiber, anti-wear performance and the boundary strength of carbon fiber are significantly improved.
The advantage of the embodiment of the present invention is as follows:
Aqueous polyurethane sizing agent provided by the invention belongs to the self-emulsifying systems of carbon fiber, preparation process is nontoxic, containing certain hydrophilic radical in molecular structure, there is good dilution stability, overcome the shortcoming of existing carbon fiber sizing agent, it is compared with common outer oil-in-water type carbon fiber sizing agent, not only containing being used for the bonding oh group of same polyurethane resin, but also basic group---the carbamate containing polyurethane material, thus add the wettability of sizing agent for carbon fiber, be more conducive to be attached to carbon fiber surface, carbon fibre composite is made to show better mechanical property.
The above is most preferred embodiment of the present invention, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. an aqueous polyurethane sizing agent, is characterized in that, comprises the component of following weight portion:
Aqueous polyurethane emulsion: 5 ~ 25 parts, deionized water: 75 ~ 95 parts.
2. aqueous polyurethane sizing agent as claimed in claim 1, it is characterized in that, described aqueous polyurethane emulsion comprises the component of following weight portion:
Dihydroxylic alcohols: 110 ~ 135 parts, isocyanates: 15 ~ 40 parts, catalyst: 0 ~ 0.01 part,
Deionized water: 225 ~ 600 parts.
3. aqueous polyurethane sizing agent as claimed in claim 2, it is characterized in that, described dihydroxylic alcohols is the combination of the polyethylene glycol of number-average molecular weight 400 ~ 2000 and the PTMG of number-average molecular weight 400 ~ 2000;
Described isocyanates is isoflurane chalcone diisocyanate, toluene di-isocyanate(TDI) or hexamethylene diisocyanate;
In described dihydroxylic alcohols, the molal quantity total amount of hydroxyl-OH and the molal quantity total amount of isocyanate group-NCO in isocyanates are than being [-OH]: [-NCO]=1.5:1 ~ 1:1.5.
4. aqueous polyurethane sizing agent as claimed in claim 2, it is characterized in that, described catalyst is dibutyl tin dilaurate.
5. aqueous polyurethane sizing agent as claimed in claim 3, it is characterized in that, the percetage by weight in the formation component of described aqueous polyurethane emulsion in addition to deionized water shared by polyethylene glycol is 5% ~ 50%.
6. a preparation method for aqueous polyurethane sizing agent, is characterized in that, comprises the steps:
(1) Waterborne Polyurethane Prepolymer is prepared;
(2) add deionized water in hydrotropism's base polyurethane prepolymer for use as, obtain aqueous polyurethane emulsion;
(3) in hydrotropism's polyaminoester emulsion, ratio adds deionized water by weight, obtains aqueous polyurethane sizing agent after stirring.
7. preparation method as claimed in claim 6, it is characterized in that, described step (1) specifically comprises the steps:
The dihydroxylic alcohols of 110 ~ 135 weight portions is added in reaction vessel, after mixing, dehydration 20 ~ 30min is vacuumized under 120 DEG C of conditions, be cooled to 70 ~ 80 DEG C, add the catalyst reaction 3 ~ 6 hours of the isocyanates of 15 ~ 40 weight portions and 0 ~ 0.01 weight portion, be cooled to 40 ~ 50 DEG C, obtain the Waterborne Polyurethane Prepolymer that end group is oh group.
8. preparation method as claimed in claim 6, it is characterized in that, described step (2) specifically comprises the steps:
Be add deionized water in the Waterborne Polyurethane Prepolymer of oh group to end group under the high-speed stirred shearing force of 1200r/min ~ 2500r/min, obtain aqueous polyurethane emulsion.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106884330A (en) * | 2017-03-24 | 2017-06-23 | 东华大学 | A kind of emulsion type carbon fiber sizing agent and its preparation method and application |
| CN107869061A (en) * | 2017-12-20 | 2018-04-03 | 苏州润弘贸易有限公司 | fluorescent type aqueous polyurethane slurry |
| CN110130109A (en) * | 2019-04-17 | 2019-08-16 | 镇江市高等专科学校 | A kind of novel carbon fiber sizing agent |
| CN110499648A (en) * | 2018-05-16 | 2019-11-26 | 骏能化工（龙南）有限公司 | A kind of aqueous polyurethane slurry |
| CN110747647A (en) * | 2019-11-07 | 2020-02-04 | 武汉纺织大学 | Antibacterial carbon fiber sizing agent emulsion and preparation method and application thereof |
| CN110903458A (en) * | 2019-12-23 | 2020-03-24 | 万华化学集团股份有限公司 | Preparation method of closed waterborne polyurethane used as aramid fiber surface treatment agent, prepared closed waterborne polyurethane and application |
| CN113026366A (en) * | 2021-05-06 | 2021-06-25 | 长春工业大学 | Bio-based polyurethane sizing agent and preparation method thereof |
| CN113550148A (en) * | 2021-08-03 | 2021-10-26 | 长春工业大学 | High-surface-energy carbon fiber water-soluble sizing agent for carbon paper and preparation method thereof |
| CN114875676A (en) * | 2022-04-21 | 2022-08-09 | 上海交通大学 | Waterborne polyurethane carbon fiber sizing agent enhanced by p-aminobenzyl methanol, and preparation method and application thereof |
| CN115450050A (en) * | 2022-09-30 | 2022-12-09 | 愿景控股有限公司 | Polyurethane emulsion sizing agent for carbon fibers |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0441779A (en) * | 1990-06-04 | 1992-02-12 | Asahi Chem Ind Co Ltd | Sized carbon fiber |
| CN101096004A (en) * | 2006-06-27 | 2008-01-02 | 深圳市海川实业股份有限公司 | Method for preparing polyurethane dispersants |
| JP2009263814A (en) * | 2008-04-25 | 2009-11-12 | Teijin Techno Products Ltd | Aromatic polyamide short-fiber bundle |
| CN101845755A (en) * | 2010-03-16 | 2010-09-29 | 天津碧海蓝天水性高分子材料有限公司 | Self-emulsifying polyurethanes epoxy sizing agent for carbon fibers and preparation method thereof |
| CN104311781A (en) * | 2014-10-29 | 2015-01-28 | 东南大学 | High-moisture-permeability aqueous polyurethane material and preparation method thereof |
| CN104628981A (en) * | 2015-02-10 | 2015-05-20 | 新纶科技（常州）有限公司 | Method for preparing waterborne polyurethane adhesive |
-
2015
- 2015-09-08 CN CN201510568396.4A patent/CN105088798A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0441779A (en) * | 1990-06-04 | 1992-02-12 | Asahi Chem Ind Co Ltd | Sized carbon fiber |
| CN101096004A (en) * | 2006-06-27 | 2008-01-02 | 深圳市海川实业股份有限公司 | Method for preparing polyurethane dispersants |
| JP2009263814A (en) * | 2008-04-25 | 2009-11-12 | Teijin Techno Products Ltd | Aromatic polyamide short-fiber bundle |
| CN101845755A (en) * | 2010-03-16 | 2010-09-29 | 天津碧海蓝天水性高分子材料有限公司 | Self-emulsifying polyurethanes epoxy sizing agent for carbon fibers and preparation method thereof |
| CN104311781A (en) * | 2014-10-29 | 2015-01-28 | 东南大学 | High-moisture-permeability aqueous polyurethane material and preparation method thereof |
| CN104628981A (en) * | 2015-02-10 | 2015-05-20 | 新纶科技（常州）有限公司 | Method for preparing waterborne polyurethane adhesive |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106884330A (en) * | 2017-03-24 | 2017-06-23 | 东华大学 | A kind of emulsion type carbon fiber sizing agent and its preparation method and application |
| CN107869061A (en) * | 2017-12-20 | 2018-04-03 | 苏州润弘贸易有限公司 | fluorescent type aqueous polyurethane slurry |
| CN110499648A (en) * | 2018-05-16 | 2019-11-26 | 骏能化工（龙南）有限公司 | A kind of aqueous polyurethane slurry |
| CN110130109A (en) * | 2019-04-17 | 2019-08-16 | 镇江市高等专科学校 | A kind of novel carbon fiber sizing agent |
| CN110747647A (en) * | 2019-11-07 | 2020-02-04 | 武汉纺织大学 | Antibacterial carbon fiber sizing agent emulsion and preparation method and application thereof |
| CN110903458A (en) * | 2019-12-23 | 2020-03-24 | 万华化学集团股份有限公司 | Preparation method of closed waterborne polyurethane used as aramid fiber surface treatment agent, prepared closed waterborne polyurethane and application |
| CN113026366A (en) * | 2021-05-06 | 2021-06-25 | 长春工业大学 | Bio-based polyurethane sizing agent and preparation method thereof |
| CN113550148A (en) * | 2021-08-03 | 2021-10-26 | 长春工业大学 | High-surface-energy carbon fiber water-soluble sizing agent for carbon paper and preparation method thereof |
| CN114875676A (en) * | 2022-04-21 | 2022-08-09 | 上海交通大学 | Waterborne polyurethane carbon fiber sizing agent enhanced by p-aminobenzyl methanol, and preparation method and application thereof |
| CN114875676B (en) * | 2022-04-21 | 2023-12-12 | 上海交通大学 | Para-aminobenzyl alcohol enhanced aqueous polyurethane carbon fiber sizing agent, preparation method and application |
| CN115450050A (en) * | 2022-09-30 | 2022-12-09 | 愿景控股有限公司 | Polyurethane emulsion sizing agent for carbon fibers |
| CN115450050B (en) * | 2022-09-30 | 2023-10-17 | 愿景控股有限公司 | Polyurethane emulsion sizing agent for carbon fibers |
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