CN102898615A - Method for modification of waterborne polyurethane by using epoxy resin - Google Patents
Method for modification of waterborne polyurethane by using epoxy resin Download PDFInfo
- Publication number
- CN102898615A CN102898615A CN2012103327764A CN201210332776A CN102898615A CN 102898615 A CN102898615 A CN 102898615A CN 2012103327764 A CN2012103327764 A CN 2012103327764A CN 201210332776 A CN201210332776 A CN 201210332776A CN 102898615 A CN102898615 A CN 102898615A
- Authority
- CN
- China
- Prior art keywords
- performed polymer
- epoxy resin
- aqueous polyurethane
- bdo
- dmpa
- 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.)
- Pending
Links
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention provides a method for modification of waterborne polyurethane by using an epoxy resin. According to the invention, TDI, N220, BDO, DMPA and E-44 are used as raw materials for preparation of a performed polymer; then HEA is added for termination of the -NCO terminal of the performed polymer; triethylamine is added for a neutralization reaction to produce a salt; a prepared double-bond terminated waterborne polyurethane emulsion can be further used as a performed polymer for a waterborne UV-cured coating or undergoes further copolymerization modification with acrylate monomers under the action of HEA. The waterborne polyurethane prepared in the invention has good mechanical properties, water resistance and solvent resistance after film forming.
Description
Technical field
The present invention relates to a kind of method of epoxy resin modified aqueous polyurethane, belong to chemical field.
Technical background
Aqueous polyurethane has been widely used in the aspects such as coatings industry, tanning industry, sizing agent as a kind of active material.Traditional aqueous polyurethane is owing to introduced hydrophilic radical, so that the water tolerance that aqueous polyurethane is filmed and solvent-resisting are relatively poor, therefore, the water-resistance property of coating and the mechanical property that improve aqueous polyurethane by modification become necessary.
Resins, epoxy has modulus height, advantage that chemical resistant properties is good, can participate in the building-up reactions of aqueous polyurethane directly, and then improves chemical resistant properties and the mechanical property of aqueous polyurethane.This paper takes full advantage of the epoxy group(ing) of Resins, epoxy and hydroxyl participates in reaction, forms multiple cross-linkedly, makes the aqueous polyurethane of epoxy resin modification, has good chemical resistant properties and mechanical property.
Summary of the invention
The method that the purpose of this invention is to provide a kind of epoxy resin modified aqueous polyurethane, the aqueous polyurethane that obtains has good chemical resistant properties and mechanical property.
For realizing above purpose, the preparation method of water tolerance aqueous polyurethane of the present invention, its step is specially:
(1) with 2,6-tolylene diisocyanate (TDI), polyether glycol (N220), BDO (BDO), dimethylol propionic acid (DMPA), Resins, epoxy (E-44) prepares performed polymer for raw material.
(2) adding Hydroxyethyl acrylate (HEA) carries out end-blocking to the end-NCO of performed polymer, reaction 50min.
(3) be cooled to 40 ℃, add triethylamine and carry out neutralization reaction generation salt, reaction 3-4min.
(4) add entry and carry out emulsification 60min, obtain the aqueous polyurethane emulsion of HEA end-blocking.
The proportioning of performed polymer raw material is in the step (1): the mol ratio of TDI and N220, DMPA, BDO, E-44 is 1.2:1-1.3:1, and BDO accounts for the 2%-3% of performed polymer quality, and DMPA accounts for the 4%-5% of performed polymer quality, and E-44 accounts for the 5%-6% of performed polymer quality.
The ratio of the amount of substance of the amount of substance of Hydroxyethyl acrylate (HEA) and excessive-NCO is 0.35 in the step (2).
The amount of substance of triethylamine is identical with the amount of substance of DMPA in the step (3).
The consumption of the middle water of step (4) is 2 times of performed polymer total mass.
The beneficial effect that the present invention produces is, this patent adopts epoxy resin modified aqueous polyurethane, the epoxy group(ing) and the hydroxyl that take full advantage of Resins, epoxy participate in reaction, form multiple cross-linked, improve chemical resistant properties and the mechanical property of aqueous polyurethane, in addition, the Hydroxyethyl acrylate of introducing in building-up process is to the base polyurethane prepolymer for use as end-blocking, make prepared emulsion contain unsaturated double-bond, can be further used as the prepolymer of aqueous ultraviolet photo-cured coating or sizing agent or under the effect of Hydroxyethyl acrylate, further carry out further modification by copolymerization with the monomer of esters of acrylic acid.
Embodiment
Embodiment 1:
Prepare performed polymer with 2,6-tolylene diisocyanate (TDI), polyether glycol (N220), BDO (BDO), dimethylol propionic acid (DMPA), Resins, epoxy (E-44) for raw material.Its proportioning is: the mol ratio of TDI and N220, DMPA, BDO, E-44 is 1.25:1, and BDO accounts for 2% of performed polymer quality, and DMPA accounts for 5% of performed polymer quality.Adding Hydroxyethyl acrylate (HEA) carries out end-blocking to the end-NCO of performed polymer, reaction 50min.Be cooled to 40 ℃, add triethylamine and carry out neutralization reaction generation salt, reaction 4min.Add entry and carry out emulsification 60min, obtain the aqueous polyurethane emulsion of the epoxy resin modification of HEA end-blocking.
Embodiment 2:
Prepare performed polymer with 2,6-tolylene diisocyanate (TDI), polyether glycol (N220), BDO (BDO), dimethylol propionic acid (DMPA), Resins, epoxy (E-44) for raw material.Its proportioning is: the mol ratio of TDI and N220, DMPA, BDO, E-44 is 1.3:1, and BDO accounts for 2% of performed polymer quality, and DMPA accounts for 5% of performed polymer quality.Adding Hydroxyethyl acrylate (HEA) carries out end-blocking to the end-NCO of performed polymer, reaction 50min.Be cooled to 40 ℃, add triethylamine and carry out neutralization reaction generation salt, reaction 4min.Add entry and carry out emulsification 60min, obtain the aqueous polyurethane emulsion of the epoxy resin modification of HEA end-blocking.
Claims (5)
1. the method for an epoxy resin modified aqueous polyurethane, it is characterized in that: step is as follows:
(1) prepares performed polymer with 2,6-tolylene diisocyanate (TDI), polyether glycol (N220), BDO (BDO), dimethylol propionic acid (DMPA), Resins, epoxy (E-44) for raw material;
(2) adding Hydroxyethyl acrylate (HEA) carries out end-blocking to the end-NCO of performed polymer, reaction 50min;
(3) be cooled to 40 ℃, add triethylamine and carry out neutralization reaction generation salt, reaction 3-4min;
(4) add entry and carry out emulsification 60min, obtain the epoxy resin modified water-based polyurethane emulsion of HEA end-blocking.
2. the method for a kind of epoxy resin modified aqueous polyurethane as claimed in claim 1, it is characterized in that: the proportioning of performed polymer raw material is in the described step (1): the mol ratio of TDI and N220, DMPA, BDO, E-44 is 1.2:1-1.3:1, BDO accounts for the 2%-3% of performed polymer quality, DMPA accounts for the 4%-5% of performed polymer quality, and E-44 accounts for the 5%-6% of performed polymer quality.
3. the method for a kind of epoxy resin modified aqueous polyurethane as claimed in claim 1 is characterized in that: the ratio of the amount of substance of the amount of substance of Hydroxyethyl acrylate (HEA) and excessive-NCO is 0.35 in the described step (2).
4. the method for a kind of epoxy resin modified aqueous polyurethane as claimed in claim 1 is characterized in that: the amount of substance of triethylamine is identical with the amount of substance of DMPA in the described step (3).
5. the method for a kind of strong epoxy resin modified aqueous polyurethane as claimed in claim 1 is characterized in that: the consumption of water is 2 times of performed polymer total mass in the described step (4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103327764A CN102898615A (en) | 2012-09-11 | 2012-09-11 | Method for modification of waterborne polyurethane by using epoxy resin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012103327764A CN102898615A (en) | 2012-09-11 | 2012-09-11 | Method for modification of waterborne polyurethane by using epoxy resin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102898615A true CN102898615A (en) | 2013-01-30 |
Family
ID=47571128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012103327764A Pending CN102898615A (en) | 2012-09-11 | 2012-09-11 | Method for modification of waterborne polyurethane by using epoxy resin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102898615A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103451942A (en) * | 2013-09-02 | 2013-12-18 | 朱文潮 | Method for preparing wool shrink resistant agent by waterborne polyurethane compound-modified by acrylate and epoxy resin |
| CN104045804A (en) * | 2014-05-30 | 2014-09-17 | 陕西科技大学 | Preparation method of aqueous light-curable polyurethane paper surface reinforcing agent |
| CN104356343A (en) * | 2014-11-04 | 2015-02-18 | 佛山市功能高分子材料与精细化学品专业中心 | Epoxy resin and castor oil double-modified polyurethane leather finishing agent and preparation method thereof |
| CN104387554A (en) * | 2014-10-30 | 2015-03-04 | 巨石集团有限公司 | Method for preparing polyurethane modified epoxy resin film forming agent |
| CN104673172A (en) * | 2015-01-27 | 2015-06-03 | 四川大学 | Thermo-sensitive type waterborne polyurethane adhesive and preparation method of thermo-sensitive type waterborne polyurethane adhesive |
| CN104946109A (en) * | 2015-06-01 | 2015-09-30 | 芜湖县双宝建材有限公司 | High-hardness water-resistant polyurethane marine coating |
| CN105199593A (en) * | 2015-11-02 | 2015-12-30 | 淄博夸克医药技术有限公司 | Modified polyurethane fireproof coating with wear resistance |
| CN107383320A (en) * | 2017-08-23 | 2017-11-24 | 南京林业大学 | The preparation method of epoxy resin modification shape memory polyurethane |
| CN107760191A (en) * | 2017-09-29 | 2018-03-06 | 东来涂料技术（上海）有限公司 | A kind of waterborne conductive priming paint applied to automobile carbon fiber and preparation method thereof |
| CN108949092A (en) * | 2018-07-26 | 2018-12-07 | 龙游恒宇鞋业有限公司 | A kind of water-borne UV-curing adhesive and its preparation method and application |
| CN111378091A (en) * | 2018-12-28 | 2020-07-07 | 财团法人工业技术研究院 | Waterborne polyurethane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438257A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylic polyurethane copolymer emulsion, its preparation method and use |
| CN1687191A (en) * | 2005-04-01 | 2005-10-26 | 合肥工业大学 | Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process |
| WO2006104111A1 (en) * | 2005-03-29 | 2006-10-05 | Nippon Polyurethane Industry Co., Ltd. | Modified water-based resin composition |
-
2012
- 2012-09-11 CN CN2012103327764A patent/CN102898615A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1438257A (en) * | 2003-03-06 | 2003-08-27 | 华南理工大学 | Acrylic polyurethane copolymer emulsion, its preparation method and use |
| WO2006104111A1 (en) * | 2005-03-29 | 2006-10-05 | Nippon Polyurethane Industry Co., Ltd. | Modified water-based resin composition |
| CN1687191A (en) * | 2005-04-01 | 2005-10-26 | 合肥工业大学 | Aqucous polyurethane modified from vinyl resin possessing structure of bisphenol A and its preparing process |
Non-Patent Citations (2)
| Title |
|---|
| 朱黎澜等: ""环氧改性水性聚氨酯的合成工艺及性能研究"", 《涂料工业》 * |
| 黄洪等: ""环氧树脂与丙烯酸酯复合改性水性聚氨酯的合成研究"", 《高校化学工程学报》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103451942A (en) * | 2013-09-02 | 2013-12-18 | 朱文潮 | Method for preparing wool shrink resistant agent by waterborne polyurethane compound-modified by acrylate and epoxy resin |
| CN104045804A (en) * | 2014-05-30 | 2014-09-17 | 陕西科技大学 | Preparation method of aqueous light-curable polyurethane paper surface reinforcing agent |
| CN104387554A (en) * | 2014-10-30 | 2015-03-04 | 巨石集团有限公司 | Method for preparing polyurethane modified epoxy resin film forming agent |
| CN104356343B (en) * | 2014-11-04 | 2017-05-17 | 佛山市功能高分子材料与精细化学品专业中心 | Epoxy resin and castor oil double-modified polyurethane leather finishing agent and preparation method thereof |
| CN104356343A (en) * | 2014-11-04 | 2015-02-18 | 佛山市功能高分子材料与精细化学品专业中心 | Epoxy resin and castor oil double-modified polyurethane leather finishing agent and preparation method thereof |
| CN104673172A (en) * | 2015-01-27 | 2015-06-03 | 四川大学 | Thermo-sensitive type waterborne polyurethane adhesive and preparation method of thermo-sensitive type waterborne polyurethane adhesive |
| CN104673172B (en) * | 2015-01-27 | 2017-04-12 | 四川大学 | Thermo-sensitive type waterborne polyurethane adhesive and preparation method of thermo-sensitive type waterborne polyurethane adhesive |
| CN104946109A (en) * | 2015-06-01 | 2015-09-30 | 芜湖县双宝建材有限公司 | High-hardness water-resistant polyurethane marine coating |
| CN105199593A (en) * | 2015-11-02 | 2015-12-30 | 淄博夸克医药技术有限公司 | Modified polyurethane fireproof coating with wear resistance |
| CN107383320A (en) * | 2017-08-23 | 2017-11-24 | 南京林业大学 | The preparation method of epoxy resin modification shape memory polyurethane |
| CN107760191A (en) * | 2017-09-29 | 2018-03-06 | 东来涂料技术（上海）有限公司 | A kind of waterborne conductive priming paint applied to automobile carbon fiber and preparation method thereof |
| CN108949092A (en) * | 2018-07-26 | 2018-12-07 | 龙游恒宇鞋业有限公司 | A kind of water-borne UV-curing adhesive and its preparation method and application |
| CN111378091A (en) * | 2018-12-28 | 2020-07-07 | 财团法人工业技术研究院 | Waterborne polyurethane and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102898615A (en) | Method for modification of waterborne polyurethane by using epoxy resin | |
| CN104788623B (en) | The preparation method of intercrossed network type aqueous polyurethane acrylate complex emulsions | |
| CN101792570B (en) | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application | |
| CN103319680B (en) | Preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate | |
| CN111116862B (en) | Hyperbranched castor oil-based aqueous UV curing prepolymer and preparation method and application thereof | |
| CN110066400B (en) | High-water-solubility modified epoxy acrylic resin and preparation method thereof | |
| RU2012143700A (en) | METHOD FOR PRODUCING LOW-VISCOSE WATER-DILUTABLE POLYURETHANE (MET) -ACRYLATES, WATER-DILUTABLE POLYURETHANE (MET) ACRYLATES CONTAINING THEIR MEANS OF COATING, APPLICATION OF SOLID-USED MEDIA | |
| CN101323886B (en) | Preparation of acrylic polymer retanning agent for highly elastic leather retanning | |
| CN104877099A (en) | Preparation method of organic fluorine modified hyperbranched waterborne polyurethane | |
| CN102993405A (en) | Epoxy resin modified waterborne polyurethane | |
| CN103588951A (en) | Preparation of high-strength hydrophobic photo-curing waterborne polyurethane nano-composite emulsion | |
| CN102702450A (en) | Preparation method of waterborne polyurethane-acrylate emulsion | |
| CN102924689A (en) | Waterborne hyper-branched polyurethane coating agent | |
| CN104341572A (en) | Preparation method of solvent-free water-based polyurethane resin | |
| CN104530374A (en) | Synthetizing method of epoxy modifying aqueous polyurethane | |
| CN103588949B (en) | Preparation method of amine-terminated hyperbranched unsaturated polyamide modified waterborne poly(urethane-acrylate) (HBP-WPUA) emulsion | |
| He et al. | Synthesis of high‐solid content sulfonate‐type polyurethane dispersion by pellet process | |
| CN104945565A (en) | Electrical aluminum gilding foil glue layer resin and preparing method thereof | |
| CN105175670A (en) | Amino resin modified waterborne polyurethane as well as preparation method and application thereof | |
| CN107760189A (en) | Preparation method of environment-friendly water-based paint | |
| CN105885010A (en) | Preparation method of high-activity water-based UV-curing fluororesin | |
| CN102898592A (en) | Preparation method for acrylate-modified waterborne polyurethane | |
| JP2011173954A (en) | Method for producing aqueous urethane-modified (meth)acrylic resin dispersion | |
| CN101423602B (en) | Method for preparing ultraviolet crosslinking active multi-propenyl multi-arm star type prepolymer | |
| CN110003480B (en) | Preparation method of cationic ultraviolet curing resin with synergistic water-soluble effect |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130130 |