CN102978918A - Method for preparing wool anti-shrinking agent from acrylic ester modified waterborne polyurethane - Google Patents
Method for preparing wool anti-shrinking agent from acrylic ester modified waterborne polyurethane Download PDFInfo
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- CN102978918A CN102978918A CN2012104734005A CN201210473400A CN102978918A CN 102978918 A CN102978918 A CN 102978918A CN 2012104734005 A CN2012104734005 A CN 2012104734005A CN 201210473400 A CN201210473400 A CN 201210473400A CN 102978918 A CN102978918 A CN 102978918A
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Abstract
A method for preparing a wool anti-shrinking agent from acrylic ester modified waterborne polyurethane comprises three steps of waterborne polyurethane prepolymer preparation, terminated type waterborne polyurethane preparation and acrylic ester modified waterborne polyurethane emulsion. The wool anti-shrinking agent has the advantages of environmental friendliness and convenience in processing, and a chlorination/resin technology is gradually replaced. The method adopts acrylic ester to modify waterborne polyurethane, so that the molecular weight is increased, and the film-forming property is improved; and moreover, the weather resistance of the anti-shrinking agent can be improved, the yellowing phenomenon is reduced, the wool appearance is improved, and the service life of the wool is prolonged.
Description
Technical field
The present invention relates to the method that a kind of acrylic ester modified water-soluble polyurethane prepares the wool shrinkproof agent, belong to chemical field.
Technical background
Wool fabric is a kind of expensive goods, and the incomparable advantage of other fabrics is arranged, as soft, good springiness, warming, gloss is soft etc.But the contracting territory property of wool makes wool textile produce easily felting when washing, and this has had a strong impact on outward appearance and the service performance of fabric.
Traditional anti-compression method mostly adopts chlorination/resin technique to process, this technology is ripe, shrinkproof result is good, but larger to the damage of wool, can cause the forfeiture of wool fabric mechanical strength, the AOX of its release can cause environmental problem, and complicated arrangement process.Comparatively speaking, the agent of aqueous polyurethane wool shrinkproof has environmental protection, advantage easy to process, and has progressively replaced chlorination/resin technique.Contain active group in the aqueous polyurethane anti-piping compound strand, form the polymer film with cross-linked network structure at wool surface after the arrangement, and with wool fibre between produce chemical bond and be connected, therefore has splendid shrinkproof result, and shrinkproof durability is fairly good, so the agent of aqueous polyurethane wool shrinkproof is by International Wool Secretariat's recommendation.
Common waterborne blocked polyurethane can rapid osmotic arrive wool fabric inside, in the even film forming of fiber surface, still, and its molecular weight, filming performance is relatively poor, affects shrinkproof result.This patent adopts the method for acrylic ester modified water-soluble polyurethane can increase molecular weight, improves simultaneously the yellowing phenomenon.
Summary of the invention
The purpose of this invention is to provide the method that a kind of acrylic ester modified water-soluble polyurethane prepares the wool shrinkproof agent.
For realizing above purpose, a kind of acrylic ester modified water-soluble polyurethane of the present invention prepares the method for wool shrinkproof agent, and its preparation process is as follows:
(1) preparation of Waterborne Polyurethane Prepolymer: prepare performed polymer take isophorone diisocyanate (IPDI), polyethylene glycol (PEG3000), BDO (BDO), dihydromethyl propionic acid (DMPA) as raw material.Add PEG3000, DMPA in the container, be warming up to 75 ℃, add IPDI and an amount of dibutyltin dilaurate catalyst, reaction 120min.In course of reaction, add 1-METHYLPYRROLIDONE to reduce viscosity.Add small molecule chain extender BDO after the reaction, reaction 90min.
(2) preparation of waterborne blocked polyurethane: adding hydroxy-ethyl acrylate (HEA) carries out end-blocking to the end-NCO of performed polymer, reaction 60min.Be cooled to 40 ℃, add triethylamine and carry out neutralization reaction generation salt, reaction 3-5min.
(3) preparation of acrylic ester modified water-soluble polyurethane emulsion: add tri (propylene glycol) diacrylate (TPGDA) and water and carry out emulsification 60min, obtain the aqueous polyurethane emulsion that is mixed with TPGDA of HEA end-blocking.This emulsion is warming up to 75 ℃, add an amount of initator azodiisobutyronitrile, make two keys of TPGDA and HEA open the emulsion that polymerization obtains acrylate and aqueous polyurethane modification by copolymerization, adding deionized water, to be mixed with solid content be 30 ~ 40% aqua, can obtain the wool shrinkproof agent.
Wherein the raw material proportioning of performed polymer is that the mol ratio of IPDI and PEG3000, DMPA, BDO is 1.8:1-2.0:1 in the step (1), and BDO accounts for the 3%-4% of performed polymer quality, and DMPA accounts for the 5%-6% of performed polymer quality.The ratio of the amount of substance of the amount of substance of hydroxy-ethyl acrylate (HEA) and excessive-NCO is 0.4 in the step (2).The consumption of tri (propylene glycol) diacrylate (TPGDA) is the 20%-30% of performed polymer gross mass in the step (3).
The beneficial effect that the present invention produces is, utilize polyurethane to be deposited on wool surface, scale layer is covered, reach the purpose that reduces along contrary frictional drop, simultaneously there is bonding point between the fiber, between polymer and wool, forms chemical bond and connect, improved the durability of felt proofing, hindered between the fiber and mutually moved, made shrinkproof result better.To contain the poor activity of 2 isocyanates larger for IPDI in the raw material that uses among the present invention, and then the accessory substance of reaction is less, can improve the quality of product.Use acrylate that aqueous polyurethane is carried out modification among the present invention, can increase molecular weight, improve filming performance, can improve the weatherability of anti-piping compound simultaneously, the yellowing phenomenon reduces to some extent, has improved the outward appearance of wool, has prolonged the service life of wool.
Embodiment
Embodiment 1
Prepare the wool shrinkproof agent with following steps:
(1) preparation of Waterborne Polyurethane Prepolymer: prepare performed polymer take isophorone diisocyanate (IPDI), polyethylene glycol (PEG3000), BDO (BDO), dihydromethyl propionic acid (DMPA) as raw material.Proportioning is that the mol ratio of IPDI and PEG3000, DMPA, BDO is 2.0:1, and BDO accounts for 4% of performed polymer quality, and DMPA accounts for 6% of performed polymer quality.Add PEG3000, DMPA in the container, be warming up to 75 ℃, add IPDI and an amount of dibutyltin dilaurate catalyst, reaction 120min.In course of reaction, add 1-METHYLPYRROLIDONE to reduce viscosity.Add small molecule chain extender BDO after the reaction, reaction 90min.
(2) preparation of waterborne blocked polyurethane: adding hydroxy-ethyl acrylate (HEA) carries out end-blocking to the end-NCO of performed polymer, and wherein the ratio of the amount of substance of the amount of substance of HEA and excessive-NCO is 0.4.Reaction 60min.Be cooled to 40 ℃, add triethylamine and carry out neutralization reaction generation salt, reaction 5min.
(3) preparation of acrylic ester modified water-soluble polyurethane emulsion: add tri (propylene glycol) diacrylate (TPGDA) and water and carry out emulsification 60min, obtain the aqueous polyurethane emulsion that is mixed with TPGDA of HEA end-blocking, wherein the consumption of TPGDA is 30% of performed polymer gross mass.This emulsion is warming up to 75 ℃, add an amount of initator azodiisobutyronitrile, make two keys of TPGDA and HEA open the emulsion that polymerization obtains acrylate and aqueous polyurethane modification by copolymerization, adding deionized water, to be mixed with solid content be 40% aqua, can obtain the wool shrinkproof agent.
Embodiment 2
Prepare the wool shrinkproof agent with following steps:
(1) preparation of Waterborne Polyurethane Prepolymer: prepare performed polymer take isophorone diisocyanate (IPDI), polyethylene glycol (PEG3000), BDO (BDO), dihydromethyl propionic acid (DMPA) as raw material.Proportioning is that the mol ratio of IPDI and PEG3000, DMPA, BDO is 1.8:1, and BDO accounts for 3% of performed polymer quality, and DMPA accounts for 5.5% of performed polymer quality.Add PEG3000, DMPA in the container, be warming up to 75 ℃, add IPDI and an amount of dibutyltin dilaurate catalyst, reaction 120min.In course of reaction, add 1-METHYLPYRROLIDONE to reduce viscosity.Add small molecule chain extender BDO after the reaction, reaction 90min.
(2) preparation of waterborne blocked polyurethane: adding hydroxy-ethyl acrylate (HEA) carries out end-blocking to the end-NCO of performed polymer, and wherein the ratio of the amount of substance of the amount of substance of HEA and excessive-NCO is 0.4.Reaction 60min.Be cooled to 40 ℃, add triethylamine and carry out neutralization reaction generation salt, reaction 5min.
(3) preparation of acrylic ester modified water-soluble polyurethane emulsion: add tri (propylene glycol) diacrylate (TPGDA) and water and carry out emulsification 60min, obtain the aqueous polyurethane emulsion that is mixed with TPGDA of HEA end-blocking, wherein the consumption of TPGDA is 25% of performed polymer gross mass.This emulsion is warming up to 75 ℃, add an amount of initator azodiisobutyronitrile, make two keys of TPGDA and HEA open the emulsion that polymerization obtains acrylate and aqueous polyurethane modification by copolymerization, adding deionized water, to be mixed with solid content be 30% aqua, can obtain the wool shrinkproof agent.
Claims (4)
1. an acrylic ester modified water-soluble polyurethane prepares the method for wool shrinkproof agent, and it is characterized in that: step is as follows:
The preparation of Waterborne Polyurethane Prepolymer: prepare performed polymer take isophorone diisocyanate (IPDI), polyethylene glycol (PEG3000), BDO (BDO), dihydromethyl propionic acid (DMPA) as raw material; Add PEG3000, DMPA in the container, be warming up to 75 ℃, add IPDI and an amount of dibutyltin dilaurate catalyst, reaction 120min; In course of reaction, add 1-METHYLPYRROLIDONE to reduce viscosity; Add small molecule chain extender BDO after the reaction, reaction 90min;
(2) preparation of waterborne blocked polyurethane: adding hydroxy-ethyl acrylate (HEA) carries out end-blocking to the end-NCO of performed polymer, reaction 60min; Be cooled to 40 ℃, add triethylamine and carry out neutralization reaction generation salt, reaction 3-5min;
(3) preparation of acrylic ester modified water-soluble polyurethane emulsion: add tri (propylene glycol) diacrylate (TPGDA) and water and carry out emulsification 60min, obtain the aqueous polyurethane emulsion that is mixed with TPGDA of HEA end-blocking; This emulsion is warming up to 75 ℃, add an amount of initator azodiisobutyronitrile, make two keys of TPGDA and HEA open the emulsion that polymerization obtains acrylate and aqueous polyurethane modification by copolymerization, adding deionized water, to be mixed with solid content be 30 ~ 40% aqua, can obtain the wool shrinkproof agent.
2. a kind of acrylic ester modified water-soluble polyurethane as claimed in claim 1 prepares the method for wool shrinkproof agent, it is characterized in that: the raw material proportioning of performed polymer is that the mol ratio of IPDI and PEG3000, DMPA, BDO is 1.8:1-2.0:1 in the described step (1), BDO accounts for the 3%-4% of performed polymer quality, and DMPA accounts for the 5%-6% of performed polymer quality.
3. a kind of acrylic ester modified water-soluble polyurethane as claimed in claim 1 prepares the method for wool shrinkproof agent, it is characterized in that: the ratio of the amount of substance of the amount of substance of hydroxy-ethyl acrylate (HEA) and excessive-NCO is 0.4 in the described step (2).
4. a kind of acrylic ester modified water-soluble polyurethane as claimed in claim 1 prepares the method for wool shrinkproof agent, it is characterized in that: the consumption of tri (propylene glycol) diacrylate (TPGDA) is the 20%-30% of performed polymer gross mass in the described step (3).
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012104734005A CN102978918A (en) | 2012-11-21 | 2012-11-21 | Method for preparing wool anti-shrinking agent from acrylic ester modified waterborne polyurethane |
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| CN2012104734005A CN102978918A (en) | 2012-11-21 | 2012-11-21 | Method for preparing wool anti-shrinking agent from acrylic ester modified waterborne polyurethane |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104153195A (en) * | 2014-08-06 | 2014-11-19 | 东华大学 | Finishing method for enabling wool fabric to have anti-felting function |
| CN104372613A (en) * | 2014-09-29 | 2015-02-25 | 东华大学 | Method for providing anti-felting function for wool fabric |
| CN108978226A (en) * | 2018-07-17 | 2018-12-11 | 江南大学 | A kind of preparation of polyurethane-modified polyacrylate class water repellent and application method |
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| WO2000044839A1 (en) * | 1999-01-28 | 2000-08-03 | Basf Coatings Ag | Coating agent consisting of at least four components, method for producing same and use thereof |
| CN101608010A (en) * | 2008-06-17 | 2009-12-23 | 上海富臣化工有限公司 | Polyether polyurethane-acrylate and preparation method thereof |
| CN102336875A (en) * | 2011-06-29 | 2012-02-01 | 江苏大学 | Preparation method of aqueous polyurethane acrylate photocureable paint |
| CN102417580A (en) * | 2011-11-01 | 2012-04-18 | 吴江市北厍盛源纺织品助剂厂 | Preparation method of waterborne polyurethane wool anti-felting treatment agent |
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2012
- 2012-11-21 CN CN2012104734005A patent/CN102978918A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| WO2000044839A1 (en) * | 1999-01-28 | 2000-08-03 | Basf Coatings Ag | Coating agent consisting of at least four components, method for producing same and use thereof |
| CN101608010A (en) * | 2008-06-17 | 2009-12-23 | 上海富臣化工有限公司 | Polyether polyurethane-acrylate and preparation method thereof |
| CN102336875A (en) * | 2011-06-29 | 2012-02-01 | 江苏大学 | Preparation method of aqueous polyurethane acrylate photocureable paint |
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| 钱帆: "UV固化水性聚氨酯丙烯酸酯的合成与性能", 《热固性树脂》, vol. 26, no. 5, 30 September 2011 (2011-09-30), pages 25 - 29 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104153195A (en) * | 2014-08-06 | 2014-11-19 | 东华大学 | Finishing method for enabling wool fabric to have anti-felting function |
| CN104153195B (en) * | 2014-08-06 | 2016-05-04 | 东华大学 | A kind of method for sorting that makes wool fabric there is felt proofing function |
| CN104372613A (en) * | 2014-09-29 | 2015-02-25 | 东华大学 | Method for providing anti-felting function for wool fabric |
| CN104372613B (en) * | 2014-09-29 | 2016-08-24 | 东华大学 | A kind of method making wool fabric have felt proofing function |
| CN108978226A (en) * | 2018-07-17 | 2018-12-11 | 江南大学 | A kind of preparation of polyurethane-modified polyacrylate class water repellent and application method |
| CN108978226B (en) * | 2018-07-17 | 2020-01-17 | 江南大学 | Preparation and application method of polyurethane modified acrylate water repellent agent |
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Application publication date: 20130320 |